Octyl and nonylphenol ethoxylates and carboxylates in wastewater and sediments by liquid chromatography/tandem mass spectrometry

This work presents an LC–MS–MS-based method for the quantitation of nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs) in water, sediment, and suspended particulate matter, and three of their carboxylated derivatives in water. The alkylphenol ethoxylates (APEOs) were analyzed using isotope dilution mass spectrometry with [¹³C₆]-labeled analogues, whereas the carboxylated derivatives were determined by external standard quantitation followed by confirmation using standard additions. The method was used to study APEO’s behavior in a wastewater treatment plant (WWTP), where total dissolved NP0-16EO concentration was reduced by approximately 99% from influent (390 μg l⁻¹) to final effluent (4 μg l⁻¹), and total OP0-5EO concentration decreased by 94% from 3.1 to 0.2 μg l⁻¹. In contrast, the carboxylated derivatives were formed during the process with NP0-1EC concentrations increasing from 1.4 to 24 μg l⁻¹. Short-chain APEOs were present in higher proportions in particulate matter, presumably due to greater affinity for solids compared to the long-chain homologues. NP (0.49 μg l⁻¹) and NP0-1EC (4.8 μg l⁻¹) were the only APEO-related compounds detected in a surface water sample from a WWTP-impacted estuary; implying that 90% of the mass was in the form of carboxylated derivatives. Sediment analysis showed nonylphenol to be the single most abundant compound in sediments from the Baltimore Harbor area, where differences in homologue distribution suggested the presence of treated effluent in some of the sites and non-treated sources in the rest.     

Concentrations of chlorine, bromine and iodine in Japanese rivers

Concentrations of halogens (Cl, Br and I) in 30 Japanese rivers were measured by ion chromatography and inductively coupled plasma mass spectrometry to understand their behavior in the terrestrial environment. Concentrations of Cl, Br and I in each river, obtained at 10 sampling points from the upper stream to the river mouth, tended to increase near the river mouth. The ranges of geometric means of Cl, Br and I in each river were 1.0–19.4 mg l⁻¹, 2.5–67.9 μg l⁻¹, and 0.18–8.34 μg l⁻¹, respectively. To compare halogen behavior, the concentration ratios, Br/Cl and I/Cl, were calculated. The Br/Cl range was (2.3–7.8) × 10⁻³ (geometric mean: 3.74 × 10⁻³), and it was nearly constant except for the Yoneshiro river. It was estimated that 60–80% of total Br in the middle to lower parts of this river was the excess Br. The Br chemical form in all the rivers is generally considered to be Br⁻. The I/Cl ratios had different trends in rivers flowing into the Japan Sea and Pacific Ocean, possibly due to the different geological features in the river catchments.     

Leaching and degradation of 21 pesticides in a full-scale model biobed

Filling and cleaning of pesticide sprayers presents a potential risk of pollution of soil and water. Three different solutions for handling sprayers have been suggested: Filling and cleaning in the field, filling and cleaning on hard surfaces with collection of the waste water, and filling and cleaning on a biobed, which is an excavation lined with clay and filled with a mixture of chopped straw, sphagnum and soil with turf on top, and with increased sorption capacity and microbial activity for degradation of the pesticides. In the present study the degradation and leaching of 21 pesticides (5 g of each) was followed in an established full-scale model biobed. Percolate was collected and analysed for pesticide residues, and the biobed material was sampled at three different depths and analysed by liquid chromatography double mass spectrometry (LC-MSMS). During the total study period of 563 days, no traces of 10 out of 21 applied pesticides were detected in the percolate (detection limits between 0.02 and 0.9 μg l⁻¹) and three pesticides were only detected once and at concentrations below 2 μg l⁻¹. During the first 198 days before second application, 14% of the applied herbicide bentazone was detected in the leachate with maximum and mean concentrations of 445 and 172 μg l⁻¹, respectively. About 2% of the initial mecoprop and fluazifop dose was detected in the percolate, with mean concentrations of 23 μg l⁻¹, while MCPA and dimethoate had mean concentrations of 3.5 and 4.7 μg l⁻¹, respectively. Leachate concentrations for the remaining pesticides were generally below the detection limit (0.02–0.9 μg l⁻¹, below 1% of applied). Sorption studies of five pesticides showed that compounds with a low K_d value appeared in the leachate. After 169 days, all pesticides in the biobed profile were degraded to a level below 50% of the calculated initial dose. Pesticides with K_oc values above 100 were primarily found in the uppermost 10 cm and degraded slowest due to the low bioavailability. The 11 most degradable pesticides were all degraded such that less than 3% remained in the biobed after 169 days.

Following second pesticide application of the biobed, leachate was sampled 215 and 365 days after the treatment. This showed the same pesticides to be leached out and at concentrations comparable to those of the first treatment. The same pesticides as after the first treatment were retained in the biobed.     

Determination of 4-tert-octylphenol, 4-nonylphenol and bisphenol A in surface waters from the Haihe River in Tianjin by gas chromatography-mass spectrometry with selected ion monitoring

The estrogenic pollutants 4-tert-octylphenol (OP), 4-nonylphenol (NP) and bisphenol A (BPA) were determined in surface water samples from the Haihe River, Tianjin, China. The analytes were extracted and concentrated from 300 ml acidified water samples by liquid–liquid extractions using dichloromethane, derivatized with trifluoroacetic anhydride, and quantified by gas chromatography–mass spectrometry (GC–MS) with selected ion monitoring (SIM). Among the samples collected from 14 sampling sites, only one sample was found to have a relatively high concentration of BPA (8.30 μg l⁻¹) and NP (0.55 μg l⁻¹). The concentrations of OP, NP and BPA in the other samples were in the range of 18.0–20.2, 106–296 and 19.1–106 ng l⁻¹, respectively. Recoveries for OP, NP and BPA in the spiked water samples were all over 80%.     

Distribution of pesticides and heavy metals in trophic chain

Determination of triazines herbicides (atrazine and simazine) by high performance liquid chromatography (HPLC) in samples of trophic chain were worked out. Determination limits of 0.5 μg g⁻¹ for atrazine, 0.8 μg g⁻¹ for simazine with pesticides recovery of 70–77% in trophic chain samples were obtained. The content of simazine in soils was in range 1.72–57.89 μg g⁻¹, in grass 5–88 μg g⁻¹, in milk 2.32–15.29 μg g⁻¹, in cereals 10.98–387 μg g⁻¹, in eggs 30.14–59.48 μg g⁻¹, for fruits: 2.45–6.19 μg g⁻¹. The content of atrazine in soils was in range 0.69–19.59 μg g⁻¹, in grass 7.85–23.85 μg g⁻¹, in cereals 1.88–43.08 μg g⁻¹. Cadmium, lead and zinc were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) in the same samples as atrazine and simazine. Determination limits for cadmium 5 × 10⁻³ μg g⁻¹, for lead 1 × 10⁻² μg g⁻¹, and for zinc 0.2 × 10⁻³ μg g⁻¹, were obtained. The content of cadmium in soil was in range 0.13–5.89 μg g⁻¹, in grass 114–627.72 × 10⁻³ μg g⁻¹, in milk 8.88–61.88 × 10⁻³ μg g⁻¹, in cereals 0.20–0.31 μg g⁻¹, in eggs 0.11–0.15 μg g⁻¹, in fruits 0.23–0.59 μg g⁻¹. The content of lead in soils was in range 0.57–151.50 μg g⁻¹, in grass 0.16–136.57 μg g⁻¹, in milk 1.16–3.74 μg g⁻¹, in cereals 1.05–5.47 μg g⁻¹, in eggs 5.79–55.87 μg g⁻¹, in fruits 21.00–87.36 μg g⁻¹. Zinc content in soil was in range 9.15–424.5 μg g⁻¹, in grass 35.20–55.87 μg g⁻¹, in milk 20.00–34.38 μg g⁻¹, in cereals 14.94–28.78 μg g⁻¹, in eggs 15.67–32.01 μg g⁻¹, in fruits 14.94–18.88 μg g⁻¹.

Described below extraction and mineralization methods for particular trophic chains allowed to determine of atrazine, simazine, cadmium, lead and zinc with good repeatability and precision. Emphasis was focused on liquid–liquid extraction and solid-phase extraction of atrazine and simazine from analysed materials, as well as, on monitoring the content of herbicides and metals in soil and along trophic chain. Higher concentration of pesticides in samples from west region of Poland in comparison to that of east region is likely related to common applying them in Western Europe in relation to East Europe. The content of metals strongly depends on samples origin (industry area, vicinity of motorways).     

Mercury deposition through litterfall in an Atlantic forest at Ilha Grande, Southeast Brazil

Atmospheric Hg transfer to the forest soil through litterfall was investigated in a primary rainforest at Ilha Grande (Southeast Brazil) from January to December 1997. Litter mass deposition reached 10.0 t ha⁻¹ y⁻¹, with leaves composing 50–84% of the total litter mass. Concentrations of Hg in the total fallen litter varied from 20 to 244 ng g⁻¹, with higher concentrations during the dry season, between June and August (225 ± 17 ng g⁻¹), and lower concentrations during the rainy season (99 ± 54 ng g⁻¹). This seasonal variability was reflected in the Hg flux through litterfall, which corresponded to a Hg input to the forest floor of 122 μg m⁻² y⁻¹, with average Hg deposition of 16.5 ± 1.5 μg m⁻² month⁻¹ during and just after the dry season (June–September) and 7.0 ± 3.6 μg m⁻² month⁻¹ in the rest of the year. The variability in meteorological conditions (determining atmospheric Hg availability to foliar scavenging) may explain the pulsed pattern of Hg deposition, since litterfall temporal variability was generally unrelated with such deposition, except by a peak in litterfall production in September. Comparisons with regional data on Hg atmospheric deposition show that litterfall promotes Hg deposition at Ilha Grande two to three orders of magnitude higher than open rainfall deposition in non-industrialized areas and approximately two times higher than open rainfall deposition in industrialized areas in Rio de Janeiro State. The observed input suggests that atmospheric Hg transfer through litterfall may explain a larger fraction of the total Hg input to forest soils in Southeast Brazil than those recorded at higher latitudes.     

Speciation and quantification of vapor phases in soy biodiesel and waste cooking oil biodiesel

This study characterizes the compositions of two biodiesel vapors, soy biodiesel and waste cooking oil biodiesel, to provide a comprehensive understanding of biodiesels. Vapor phases were sampled by purging oil vapors through thermal desorption tubes which were then analyzed by the thermal desorption/GC/MS system. The results show that the compounds of biodiesel vapors can be divided into four groups. They include methyl esters (the main biodiesel components), oxygenated chemicals, alkanes and alkenes, and aromatics. The first two chemical groups are only found in biodiesel vapors, not in the diesel vapor emissions. The percentages of mean concentrations for methyl esters, oxygenated chemicals, alkanes and alkenes, and aromatics are 66.1%, 22.8%, 4.8% and 6.4%, respectively for soy biodiesel, and 35.8%, 35.9%, 27.9% and 0.3%, respectively for waste cooking oil biodiesel at a temperature of 25 ± 2 °C. These results show that biodiesels have fewer chemicals and lower concentrations in vapor phase than petroleum diesel, and the total emission rates are between one-sixteenth and one-sixth of that of diesel emission, corresponding to fuel evaporative emissions of loading losses of between 106 μg l⁻¹ and 283 μg l⁻¹. Although diesels generate more vapor phase emissions, biodiesels still generate considerable amount of vapor emissions, particularly the emissions from methyl esters and oxygenated chemicals. These two chemical groups are more reactive than alkanes and aromatics. Therefore, speciation and quantification of biodiesel vapor phases are important.     

The use of physiological characteristics for comparison of organic compounds phytotoxicity

The influence of intact (FLT) and photomodified (phFLT) fluoranthene (0.05, 0.5 and 5 μmol l⁻¹) and herbicide Basagran (5, 20, 35 and 50 nmol l⁻¹) on the germination, growth of seedlings and photosynthetic processes in pea plants (Pisum sativum L., cv. Garde) was investigated. The germination was significantly inhibited already by the lowest concentration (0.05 μmol l⁻¹) of FLT and phFLT, while Basagran caused inhibition only in higher concentrations (35 and 50 nmol l⁻¹). The growth of roots was significantly inhibited by higher concentration 5 μmol l⁻¹ of both FLT and phFLT and the shoot of seedlings was significantly influenced only by photomodified form. The length of root and shoot was inhibited already by concentration 5 nmol l⁻¹ of Basagran. Organic compounds applied on chloroplasts suspension influenced primary photochemical processes of photosynthesis. In chlorophyll fluorescence parameters, the significant increase of F₀ values and the decrease of F_V/F_M and Φ_II values by application of FLT (0.5 and 5 μmol l⁻¹) and phFLT (0.05, 0.5 and 5 μmol l⁻¹) was recorded. The maximum capacity of PSII (F_V/F_M) was influenced by the highest (50 nmol l⁻¹) and the effective quantum yield of PSII (Φ_II) already by the lowest (5 nmol l⁻¹) concentration of Basagran. Hill reaction activity decreased and was significantly inhibited by higher concentration (0.5 and 5 μmol l⁻¹) of FLT and phFLT and already by the lowest concentration (5 nmol l⁻¹) of Basagran.     

Trace elements in atmospheric particulate matter over a coal burning power production area of western Macedonia, Greece

Total suspended particle (TSP) concentrations were determined in the Eordea basin (western Macedonia, Greece), an area with intensive lignite burning for power generation. The study was conducted over a one-year period (November 2000–November 2001) at 10 sites located at variable distances from the power plants. Ambient TSP samples were analyzed for 27 major, minor and trace elements. Annual means of TSP concentrations ranged between 47 ± 33 μg m⁻³ and 110 ± 50 μg m⁻³ at 9 out of the 10 sites. Only the site closest to the power stations and the lignite conveyor belts exhibited annual TSP levels (210 ± 97 μg m⁻³) exceeding the European standard (150 μg m⁻³, 80/779/EEC). Concentrations of TSP and almost all elemental components exhibited significant spatial variations; however, the elemental profiles of TSP were quite similar among all sites suggesting that they are affected by similar source types. At all sites, statistical analysis indicated insignificant (P < 0.05) seasonal variation for TSP concentrations. Some elements (Cl, As, Pb, Br, Se, S, Cd) exhibited significantly higher concentrations at certain sites during the cold period suggesting more intense emissions from traffic, domestic heating and other combustion sources. On the contrary, concentrations significantly higher in the warm period were found at other sites mainly for crustal elements (Ti, Mn, K, P, Cr, etc.) suggesting stronger influence from soil resuspension and/or fly ash in the warm months. The most enriched elements against local soil or road dust were S, Cl, Cu, As, Se, Br, Cd and Pb, whereas negligible enrichment was found for Ti, Mn, Mg, Al, Si, P, Cr. At most sites, highest concentrations of TSP and elemental components were associated with low- to moderate-speed winds favoring accumulation of emissions from local sources. Influences from the power generation were likely at those sites located closest to the power plants and mining activities.     

Utilization and degradation of imazaquin by a naturally occurring isolate of Arthrobacter crystallopoietes

A species of bacteria that is capable of utilizing imazaquin as the sole carbon source was isolated from soil with repeated imazaquin applications, and was identified as Arthrobacter crystallopoietes (designated as strain “WWX-1”). This isolate degrades imazaquin as high as 200 μg ml⁻¹, and the estimated dissipation half-lives increased from 1.51 d for the treatment at 50 μg ml⁻¹ to 4.75 d for 200 μg ml⁻¹. Optimal growth of WWX-1 in mineral salt medium with 50 μg ml⁻¹ imazaquin was obtained at 35 °C and a pH of 5.0. Growth of WWX-1 was also observed in mineral salt medium with the addition of other imidazolinone herbicides such as imazethapyr and imazapyr, but not with different classes of herbicides such as metsulfuron-methyl. Two imazaquin metabolites were detected, and spectral analysis with HPLC–MS, ¹H NMR, and IR revealed one metabolite with a molecular weight (MW) of 199 as quinoline-2,3-dicarboxylic anhydride. We propose that A. crystallopoietes (WWX-1) could serve as an efficient biodegradation system for remediation of water and soils that are heavily contaminated with imazaquin or other structurally similar chemicals.     

Selective adsorption of phenanthrene dissolved in surfactant solution using activated carbon

Selective adsorption of a hazardous hydrophobic organic compound (HOC) by activated carbon as a means of recovering surfactants after a soil washing process was investigated. As a model system, phenanthrene was selected as a representative HOC and Triton X-100 as a nonionic surfactant. Three activated carbons that differed in size (Darco 20–40 (D20), 12–20 (D12) and 4–12 (D4) mesh sizes) were used in adsorption experiments. Adsorption of surfactant onto activated carbon showed a constant maximum above the critical micelle concentration, which were 0.30, 0.23, 0.15 g g⁻¹ for D20, D12, and D4, respectively. Selectivity for phenanthrene to Triton X-100 was much higher than 1 over a wide range of activated carbon doses (0–6 g l⁻¹) and initial phenanthrene concentrations (10–110 mg l⁻¹). Selectivity generally increased with decreasing particle size, increasing activated carbon dose, and decreasing initial concentration of phenanthrene. The highest selectivity was 74.9, 57.3, and 38.3 for D20, D12, and D4, respectively, at the initial conditions of 10 mg l⁻¹ phenanthrene, 5 g l⁻¹ Triton X-100 and 1 g l⁻¹ activated carbon. In the case of D20 at the same conditions, 86.5% of the initial phenanthrene was removed by sorption and 93.6% of the initial Triton X-100 remained in the solution following the selective adsorption process. The results suggest that the selective adsorption by activated carbon is a good alternative for surfactant recovery in a soil washing process.     

Isoprene emission from tropical trees in Okinawa Island, Japan

This study surveyed isoprene emission from 42 indigenous and exotic tropical trees in subtropic Okinawa, Japan. Of the 42 trees studied, 4 emitted isoprene at a rate in excess of 20 μg g⁻¹ h⁻¹, and 28 showed the rates of 1–10 μg g⁻¹ h⁻¹. The remainder emitted less than 1 μg g⁻¹ h⁻¹. The majority of trees in this study may therefore fall within the lower emitting species. However, species in Moraceae that is indigenous in Okinawa emitted isoprene at relatively higher rates with an average of 14.2 μg g⁻¹ h⁻¹. The highest emission rate of 107.1 μg g⁻¹ h⁻¹ for Ficus virgata yielded the area basis rate of 47.4 nmol m⁻² s⁻¹, which is almost equivalent to the rate of high emitting species. Furthermore, a linear relationship between light intensity and isoprene emission was noted with Ficus virgata up to 1700 μmol m⁻² s⁻¹. These findings may show the potential importance of subtropical areas as sources of isoprene to the atmosphere.     

Methane fluxes from tundra soils and snowpack in the maritime Antarctic

Methane fluxes were measured from three exposed tundra sites and four snowpack sites on the Fildes Peninsula in the maritime Antarctic in the summertime of 2002. The average fluxes at two normal tundra sites were −15.3 μg m⁻² h⁻¹ and −14.3 μg m⁻² h⁻¹, respectively. The fluxes from tundra site with fresh penguin dropping addition showed positive values with the average of 36.1 μg m⁻² h⁻¹, suggesting that the deposition of fresh droppings greatly enhanced CH₄ emissions from the poor Antarctic tundra during penguin breeding periods. The summertime variation in CH₄ flux was correlated with surface ground temperature and the precipitation. The correlation between the flux and PT₀, which is the product of the precipitation and surface ground temperature, was quite strong. The diurnal cycle of CH₄ flux from the tundra soils was not obtained due to local fluky weather conditions. The fluxes through four snowpack sites were also obtained by the vertical CH₄ concentration gradient and their average fluxes were −46.5 μg m⁻² h⁻¹, −28.2 μg m⁻² h⁻¹, −46.4 μg m⁻² h⁻¹ and −17.9 μg m⁻² h⁻¹, respectively, indicating that tundra soils under snowpack also consume atmospheric CH₄ in the maritime Antarctic; therefore these fluxes could constitute an important part of the annual CH₄ budget for Antarctic tundra ecosystem.     

Arsenic removal from water employing heterogeneous photocatalysis with TiO2 immobilized in PET bottles

Arsenic oxidation (As(III) to As(V)) and As(V) removal from water were assessed by using TiO₂ immobilized in PET (polyethylene terephthalate) bottles in the presence of natural sunlight and iron salts. The effect of many parameters was sequentially studied: TiO₂ concentration of the coating solution, Fe(II) concentration, pH, solar irradiation time; dissolved organic carbon concentration. The final conditions (TiO₂ concentration of the coating solution: 10%; Fe(II): 7.0 mg l⁻¹; solar exposure time: 120 min) were applied to natural water samples spiked with 500 μg l⁻¹ As(III) in order to verify the influence of natural water matrix. After treatment, As(III) and total As concentrations were lower than the limit of quantitation (2 μg l⁻¹) of the voltammetric method used, showing a removal over 99%, and giving evidence that As(III) was effectively oxidized to As(V). The results obtained demonstrated that TiO₂ can be easily immobilized on a PET surface in order to perform As(III) oxidation in water and that this TiO₂ immobilization, combined with coprecipitation of arsenic on Fe(III) hydroxides(oxides) could be an efficient way for inorganic arsenic removal from groundwaters.     

Fate of cancerostatic platinum compounds in biological wastewater treatment of hospital effluents

The present work focuses on the fate of two cancerostatic platinum compounds (CPC), cisplatin and carboplatin, as well as of two inorganic platinum compounds, [PtCl₄]²⁻ and [PtCl₆]²⁻ in biological wastewater treatment. Laboratory experiments modelling adsorption of these compounds onto activated sludge showed promising specific adsorption coefficients K_D and K_OC and Freundlich adsorption isotherms. However, the adsorption properties of the investigated substances were differing significantly. Adsorption decreased following the order cisplatin > [PtCl₆]²⁻ > [PtCl₄]²⁻ > carboplatin. Log K_D-values were ranging from 2.5 to 4.3 , log K_OC from 3.0 to 4.7.

A pilot membrane bioreactor system (MBR) was installed in a hospital in Vienna and fed with wastewater from the oncologic in-patient treatment ward to investigate CPC-adsorption in a sewage treatment plant. During three monitoring periods Pt-concentrations were measured in the influent (3–250 μg l⁻¹ Pt) and the effluent (2–150 μg l⁻¹ Pt) of the treatment plant using ICP-MS. The monitoring periods (duration 30 d) revealed elimination efficiencies between 51% and 63% based on averaged weekly input–output budgets. The derived log K_D-values and log K_OC-values ranged from 2.4 to 4.8 and from 2.8 to 5.3, respectively. Species analysis using HPLC-ICP-MS proofed that mainly carboplatin was present as intact drug in the influent and – due to low log K_D – in the effluent of the MBR.     

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.     

Relationship between the loading rate of inorganic mercury to aquatic ecosystems and dissolved gaseous mercury production and evasion

The purpose of our study was to test the hypothesis that dissolved gaseous mercury (DGM) production and evasion is directly proportional to the loading rate of inorganic mercury [Hg(II)] to aquatic ecosystems. We simulated different rates of atmospheric mercury deposition in 10-m diameter mesocosms in a boreal lake by adding multiple additions of Hg(II) enriched with a stable mercury isotope (²⁰²Hg). We measured DGM concentrations in surface waters and estimated evasion rates using the thin-film gas exchange model and mass transfer coefficients derived from sulfur hexafluoride (SF₆) additions. The additions of Hg(II) stimulated DGM production, indicating that newly added Hg(II) was highly reactive. Concentrations of DGM derived from the experimental Hg(II) additions (“spike DGM”) were directly proportional to the rate of Hg(II) loading to the mesocosms. Spike DGM concentrations averaged 0.15, 0.48 and 0.94 ng l⁻¹ in mesocosms loaded at 7.1, 14.2, and 35.5 μg Hg m⁻² yr⁻¹, respectively. The evasion rates of spike DGM from these mesocosms averaged 4.2, 17.2, and 22.3 ng m⁻² h⁻¹, respectively. The percentage of Hg(II) added to the mesocosms that was lost to the atmosphere was substantial (33–59% over 8 weeks) and was unrelated to the rate of Hg(II) loading. We conclude that changes in atmospheric mercury deposition to aquatic ecosystems will not change the relative proportion of mercury recycled to the atmosphere.     

A summary of total mercury concentrations in flora and fauna near common contaminant sources in the Gulf of Mexico

Total mercury concentrations are summarized for environmental media and biota collected from near-coastal areas, several impacted by contaminant sources common to the Gulf of Mexico. Water, sediment, fish, blue crabs, oysters, clams, mussels, periphyton and seagrasses were collected during 1993–2002 from targeted areas affected by point and non-point source contaminants. Mean concentrations in water and sediment were 0.02 (±1 standard deviation = 0.06) μg l⁻¹ and 96.3 (230.8) ng g⁻¹ dry wt, respectively. Mean total mercury concentrations in fish, blue crabs, brackish clams and mussels were significantly greater than those in sediment, seagrass, colonized periphyton and oysters. Concentrations (ng g⁻¹ dry wt) averaged 23.1 (two seagrass species), 220.1 (oysters), 287.8 (colonized periphyton), 604.0 (four species of freshwater mussels), 772.4 (brackish clam), 857.9 (blue crabs) and 933.1 (nine fish species). Spatial, intraspecific and interspecific variability in results limited most generalizations concerning the relative mercury contributions of different stressor types. However, concentrations were significantly greater for some biota collected from areas receiving wastewater discharges and golf course runoff (fish), agricultural runoff (oysters) and urban stormwater runoff (colonized periphyton and sediment). Marine water quality criteria and proposed sediment quality guidelines were exceeded in 1–12% of total samples. At least one seafood consumption guideline, criteria or screening value were exceeded in edible tissues of blue crabs (6% total samples) and nine fish species (8–33% total samples) but all residues were less than the US Federal Drug Administration action limit of 1.0 ppm and the few reported toxic effect concentrations available for the targeted biota.     

Compound-specific chlorine isotope analysis of polychlorinated biphenyls isolated from Aroclor and Clophen technical mixtures

The combined electrochemical oxidation-solar-light/immobilized TiO₂ film process was conducted to degrade an azo dye, Reactive Black 5 (RB5). The toxicity was also monitored by the Vibrio fischeri light inhibition test. The electrochemical oxidation rapidly decolorized RB5 (55, 110 μM) with a supporting electrolyte of 2 g l⁻¹ NaCl at current density 277 A m⁻² and pH 4. However, TOC mineralization and A₃₁₀ removal were low. Additionally, the treated solution showed high biotoxicity. RB5 at 110 μM significantly retarded the de-colorization efficiency by using the solar-light/immobilized TiO₂ film process. The combined electrochemical oxidation-solar-light/immobilized TiO₂ process effectively increased the removal of color, A₃₁₀, and TOC. The toxicity was also significantly reduced after 3 h of solar irradiation. The results indicated that the low-cost combined process is a potential technique for rapid treatment of RB5.     

Degradation of organic pollutants in Mediterranean forest soils amended with sewage sludge

The degradation of two groups of organic pollutants in three different Mediterranean forest soils amended with sewage sludge was studied for nine months. The sewage sludge produced by a domestic water treatment plant was applied to soils developed from limestone, marl and sandstone, showing contrasting alkalinity and texture. The compounds analysed were: linear alkylbenzene sulphonates (LAS) with a 10–13 carbon alkylic chain, and nonylphenolic compounds, including nonylphenol (NP) and nonylphenol ethoxylates with one and two ethoxy groups (NP1EO + NP2EO). These compounds were studied because they frequently exceed the limits proposed for sludge application to land in Europe. After nine months, LAS decomposition was 86–96%, and NP + NP1EO + NP2EO decomposition was 61–84%, which can be considered high. Temporal trends in LAS and NP + NP1EO + NP2EO decomposition were similar, and the concentrations of both types of compounds were highly correlated. The decomposition rates were higher in the period of 6–9 months (summer period) than in the period 0–6 months (winter + spring period) for total LAS and NP + NP1EO + NP2EO. Differences in decay rates with regard to soil type were not significant. The average values of decay rates found are similar to those observed in agricultural soils.