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.     

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.     

Characterization of atmospheric particulate and metallic elements at Taichung Harbor near Taiwan Strait during 2004-2005

Air aerosol samples for TSP (total suspended particulate), coarse particulate (particle matter with aerodynamical diameter 2.5–10 μm, PM_2.5–10), fine particulate (particle matter with aerodynamical diameter <2.5 μm, PM_2.5) and metallic elements were collected during March 2004 to January 2005 at TH (Taichung Harbor) in central Taiwan. The seasonal variation average concentration of TSP (total suspended particulate), coarse particulate (particle matter with aerodynamical diameter 2.5–10 μm, PM_2.5–10) and fine particulate (particle matter with aerodynamical diameter <2.5 μm, PM_2.5) were in the range 132–171.1 μg m⁻³ and 43–49.5 μg m⁻³, respectively. Seasonal variation of metallic elements Cu, Mn, Zn and Fe in the TSP (total suspended particulate) shows that higher concentration was observed during spring. Seasonal variation of metallic elements Pb, Cr and Mg in the TSP (total suspended particulate) shows that higher concentration was observed during winter. The average metallic element TSP (total suspended particulate) concentration order was Fe > Zn > Mg > Cu > Cr > Mn > Pb in spring. In addition, at the TH sampling site, the average concentration variation of TSP (total suspended particulate) displayed the following order: spring > winter > autumn > summer. However, the average concentration variation of coarse particulate (particle matter with aerodynamical diameter 2.5–10 μm, PM_2.5–10) displayed the following order: spring > winter > summer > autumn. Finally, the average concentration variations of fine particulate (particle matter with aerodynamical diameter <2.5 μm, PM_2.5) were in the following order: winter > spring > summer > autumn at the TH sample site.     

Nitrous oxide emissions from tundra soil and snowpack in the maritime Antarctic

The nitrous oxide emissions were measured at three tundra sites and one snowpack on the Fildes Peninsula in the maritime Antarctic in the summertime of 2002. The average fluxes at two normal tundra sites were 1.1 ± 2.2 and 0.6 ± 1.7 μg N₂O m⁻² h⁻¹, respectively. The average flux from tundra soil site with penguin dropping addition was 3.7 ± 2.0 μg N₂O m⁻² h⁻¹, 3–6 times those from the normal tundra soils, suggesting that the deposition of fresh droppings enhanced N₂O emissions during penguin breeding period. The summer precipitation had an important effect on N₂O emissions; the flux decreased when heavy precipitation occurred. The diurnal cycle of the N₂O fluxes from Antarctic tundra soils was not obtained due to local fluky weather conditions. The N₂O fluxes through four snowpack sites were obtained by the vertical N₂O concentration gradient and their average fluxes were 0.94, 1.36, 0.81 and 0.85 μg N₂O m⁻² h⁻¹, respectively. The tundra soils under snowpack emitted N₂O in the maritime Antarctic and increased local atmospheric N₂O concentrations; therefore these fluxes could constitute an important part of the annual N₂O budget for Antarctic tundra ecosystem.     

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.     

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).     

Release flux of mercury from different environmental surfaces in Chongqing, China

An investigation was conducted to estimate mercury emission to the atmosphere from different environmental surfaces and to assess its contribution to the local mercury budget in Chongqing, China. Mercury flux was measured using dynamic flux chamber (DFC) at six soil sites of three different areas (mercury polluted area, farmland and woodland) and four water surfaces from August 2003 to April 2004. The mercury emission fluxes were 3.5 ± 1.2–8.4 ± 2.5 ng m⁻² h⁻¹ for three shaded forest sites, 85.8 ± 32.4 ng m⁻² h⁻¹ for farming field, 12.3 ± 9.8–733.8 ± 255 ng m⁻² h⁻¹ for grassland sites, and 5.9 ± 12.6–618.6 ± 339 ng m⁻² h⁻¹ for water surfaces. Mercury exchange fluxes were generally higher from air/water surfaces than from air/soil surfaces. The mercury negative fluxes were found in tow soil sites at overcast days (mean = −6.4 ± 1.5 ng m⁻² h⁻¹). The diurnal and seasonal variations of mercury flux were observed in all sites. The mercury emission responded positively to the solar radiation, but negatively to the relative humidity. The mercury flux from air/soil surfaces was significantly correlated with soil temperature, which was well described by an Arrhenius-type expression with activation energy of 31.1 kcal mol⁻¹. The annual mercury emission to the atmosphere from land surface is about 1.787 t of mercury in Chongqing.     

Determination and distribution characteristics of degradation products of nonylphenol polyethoxylates in the rivers of Taiwan

Concentrations of degradation products of nonylphenol polyethoxylates (NPEOs) were analyzed in river water samples in order to determine the distribution characteristic of these alkylphenolic compounds in 18 major rivers of Taiwan. The degradation products of NPEOs were detected in all river samples, with the dicarboxylates alkylphenolic degradation products (CAPEC) being detected most frequently and at the highest concentrations. Concentrations of NP and NP1EO in rivers ranged from n.d. to 5.1 μg l⁻¹ and n.d. to 0.5 μg l⁻¹, respectively. The total concentrations of shortened carboxylates (i.e., NP1EC + NP2EC + NP3EC) and dicarboxylates alkylphenolic degradation products (CAP1EC + CAP2EC) ranged from n.d. to 63.6 μg l⁻¹ and n.d. to 94.6 μg l⁻¹, respectively. Concentrations of NP2EC, NP3EC and all CAPEC residues were determined semi-quantitatively by comparing with the internal standard. Significantly higher concentrations of CAPEC residues were detected in the river waters as compared to those of NP, NP1EO and NPEC degradation products and the average proportions of these compounds in the samples of the rivers were as follows: NP + NP1EO was 5 ± 2.5%, total NPEC was 25 ± 12%, and total CAPEC was 70 ± 12%. The high concentration ratios of CAPEC/NPEC illustrate that aerobic biodegradation plays a main route in the fate of NPEO in the rivers of Taiwan.     

Monoterpene emissions and carbonyl compound air concentrations during the blooming period of rape (Brassica napus)

An increasing percentage of agricultural land in Germany is used for oil seed plants. Hence, rape has become an important agricultural plant (in Saxony 1998: 12% of the farmland) in the recent years. During flowering of rape along with intensive radiation and high temperatures, a higher production and emission of biogenic VOC was observed. The emissions of terpenes were determined and more importantly, high concentrations of organic carbonyl compounds were observed during this field experiment. All measurements of interest have been carried out during two selected days with optimal weather conditions. It is found that the origin or the mechanism of formation of different group of compounds had strong influence on the day to day variation of their concentrations. The emission flux of terpenes from flowering rape plants was determined to be 16–32 μg h⁻¹ m⁻² (30–60 ng h⁻¹ per g dry plant––540–1080 ng h⁻¹ per plant), in total. Limonene, -thujene and sabinene were the most important compounds (about 60% of total terpenes). For limonene and sabinene reference emission rates (M_S) and temperature coefficients were determined: β_limonene=0.108 K⁻¹ and M_S=14.57 μg h⁻¹ m⁻²; β_sabinene=0.095 K⁻¹ and M_S=5.39 μg h⁻¹ m⁻².

The detected carbonyl compound concentrations were unexpectedly high (maximum formaldehyde concentration was 18.1 ppbv and 3.4 ppbv for butyraldehyde) for an open field. Possible reasons for these concentrations are the combination of primary emission from the plants induced by high temperature and high ozone stress, the secondary formation from biogenically and advected anthropogenically emitted VOC at high radiation intensities and furthered by the low wind speeds at this time.     

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.     

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.     

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.     

The enhancement of photodegradation efficiency using Pt-TiO2 catalyst

The residues from the extraction of lead/zinc (Pb/Zn) ores of most Pb/Zn mines are permanently stored in tailings ponds, which require revegetation to reduce their environmental impact. This can only be done if the main constraints on plant establishment are evaluated. This can readily be done by field and greenhouse studies.

To test this, the properties of different tailings from Lechang Pb/Zn mine located at the north of Guangdong Province in southern China have been studied. Physical and chemical properties including concentrations of metals (Pb, Zn, Cd and Cu) in the tailings and soils collected from different sites have been measured. The results showed that tailings contain low nitrogen (0.016–0.075%), low-organic matter (0.58–1.78%), high salt (3.55–13.85 dS/m), and high total and diethylene–tetramine–pentaacetic acid (DTPA)-extractable metal concentrations (total: 1019–1642 μg g⁻¹ Pb, 3078–6773 μg g⁻¹ Zn, 8–23 μg g⁻¹ Cd, and 85–192 μg g⁻¹ Cu; DTPA-extractable: 59–178 μg g⁻¹ Pb, 21–200 μg g⁻¹ Zn, 0.30–1.5 μg g⁻¹ Cd, and 4.3–12 μg g⁻¹ Cu). Aqueous extracts of tailings/soils (10%, 20% and 30%, w/v) from different sites were prepared for testing their effects on seed germination and root elongation of a vegetable crop Brassica chinensis and a grass species Cynodon dactylon. It was found that root elongation provided a better evaluation of toxicity than seed germination. The ranking of toxicity using root elongation was: high-sulfur tailings>tailingdam>sparsely vegetated tailings>densely vegetated tailings>mountain soil for both plants. This order was consistent with DTPA-extractable Pb contents in the tailings and soils. B. chinensis seedlings were then grown in the mixtures of different proportions of tailings and farm soil for 4 weeks, and the results (dry weights of seedlings) were in line with the root elongation test. All these demonstrated that heavy metal toxicity, especially available Pb, low content of nutrient, and poor physical structure were major constraints on plant establishment and colonization on the Pb/Zn mine tailings.     

Mercury in air in an area impacted by strong industrial activities

The concentrations of total gaseous mercury (TGM) and its relevant environmental parameters were measured at a highly industrialized area in the Ban Wall industrial complex (BWIC) in An San city, Korea from March to May 2005. The mean concentrations of Hg measured during the entire study period were computed to be 6.32 ± 8.56 ng m⁻³ (range of 2.32–181 ng m⁻³; N = 1160). Due to the effects of strong man-made activities, the significantly high Hg concentration levels (e.g., at or above 10 ng m⁻³) comprised about 7.5% of all data with the mean of 21.8 ± 26.3 ng m⁻³ (N = 87). By separating the data into daytime and nighttime periods, the Hg values exhibited a notable daytime enhancement possibly due to strong man-made activities during working hours. The results of the correlation analysis indicated the possible relationship between the Hg concentration and the temperature as well as several pollutant species (e.g., NO₂ and NO_x). Evaluation of the Hg data in relation with the air mass transport pattern confirms that the Hg concentration levels in this industrial area are affected most eminently by local, rather than distant, pollution sources.     

A chemical and toxicological profile of Dutch North Sea surface sediments

Chemical and toxicological profiles were assessed in surface sediments (fraction <63 μm) from the southern North Sea. In extracts of freeze-dried samples, polybrominated biphenyl (PBB), Irgarol 1051 and phthalate concentrations were below the respective detection limits (except di(2-ethylhexyl)phthalate, which was between 170 and 3300 μg kg⁻¹ dry weight (dw)). Hexabromocyclododecane (HBCD) concentrations were between 0.8 and 6.9 μg kg⁻¹ dw, with highest concentrations at river mouths. Polybrominated diphenylethers (PBDE) concentrations were 0.4–0.6 μg kg⁻¹ dw, decabromodiphenylether (BDE209) 1–32 μg kg⁻¹ dw. The ratio BDE209/PCB153 was used as a tracer for recent emissions, and pointed towards a BDE209 source in the Western Scheldt’s upper estuary. PCBs and PAHs were between 0.19–4.7 and 2.6–200 μg kg⁻¹ dw respectively and generally had highest concentrations at near-shore locations and river mouths.

Responses in the Microtox broad-spectrum and the Mutatox genotoxicity assays were generally low, with near-shore locations giving higher responses. The umu-C genotoxicity and the ER-CALUX assay for estrogenicity showed no response, with the exception of one near-shore location (IJmuiden outer harbour, ER-CALUX).

Highest dioxin-like toxicity (DR-CALUX) was found at near-shore locations, in the outflow of the Rhine/Meuse estuary including a dumping site of harbour sludge. At the Oyster Grounds, DR-CALUX responses appeared to be linked to the occurrence of larger PAHs (4–6 rings). A new, non-destructive clean up procedure resulted in significantly higher DR-CALUX responses than the current protocol. The Dutch legislation on disposal of harbour sludge at sea, dictates the use of the conventional clean up procedure. Our results therefore indicate that probably more dioxin-like toxicity associated with harbour sludge is disposed off at sea than assumed.     

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.     

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.     

Cold season CH4, CO2 and N2O fluxes from freshwater marshes in northeast China

Cold season (winter and thaw) CH₄, CO₂ and N₂O fluxes from freshwater marshes (47°35′N, 133°31′E, Northeast China) were measured, using the static chamber method. The mean CH₄ and CO₂ fluxes from Carex lasiocarpa (Cl) were 0.5 ± 0.19 and 6.23 ± 1.36 mg C m⁻² h⁻¹, respectively, and those from Deyeuxia angustifoli (Da) were 0.18 ± 0.15 and 5.22 ± 2.48 mg C m⁻² h⁻¹, respectively in winter. There was no significant difference between Cl and Da (p > 0.05). The contributions of winter CH₄ fluxes were about 5.5% and 3% in the Cl and Da, respectively. Marshes are an important potential N₂O sink in winter season in northeast China. During thaw, the CH₄ and CO₂ emissions rapidly increased, 4.5–6 times of winter emissions. Wetland became a source of N₂O. Cold season gases flux from northern wetlands play an important role in the seasonal gas exchange.     

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.