Sorption-desorption behavior of polybrominated diphenyl ethers in soils

Polybrominated diphenyl ethers (PBDEs) are flame retardants that are commonly found in commercial and household products. These compounds are considered persistent organic pollutants. In this study, we used 4,4′-dibromodiphenyl ether (BDE-15) as a model compound to elucidate the sorption and desorption behavior of PBDEs in soils. The organic carbon-normalized sorption coefficient (K_OC) of BDE-15 was more than three times higher for humin than for bulk soils. However, pronounced desorption hysteresis was obtained mainly for bulk soils. For humin, increasing concentration of sorbed BDE-15 resulted in decreased desorption. Our data illustrate that BDE-15 and probably other PBDEs exhibit high sorption affinity to soils. Moreover, sorption is irreversible and thus PBDEs can potentially accumulate in the topsoil layer. We also suggest that although humin is probably a major sorbent for PBDEs in soils, other humic materials are also responsible for their sequestration.     

PCDD/F and dioxin-like PCB in Hong Kong air in relation to their regional transport in the Pearl River Delta region

PCDD/F and dioxin-like PCB were measured in 142 air samples of Hong Kong. The annual average PCDD/F and dioxin-like PCB concentrations obtained for Hong Kong air at Tap Mun (PCDD/F: 1724+/-1984; dioxin-like PCB: 1572+/-1170 fg m(-3)), Yuen Long (PCDD/F: 2927+/-2695; dioxin-like PCB: 4331+/-1962 fg m(-3)) and Tsuen Wan (PCDD/F: 1875+/-1502; dioxin-like PCB: 2972+/-1510 fg m(-3)) from January 2004 to March 2005 were comparable to other urban centers around the world and were within the Japanese and USA ambient air quality guidelines. A clear seasonal pattern was observed for PCDD/F, generally with a 50-60 times higher air concentration in winter when background northerly wind was weaker and land-sea breeze prevailed, resulting in regional transport; and a lower concentration in summer, due to the inflow of clean oceanic southeasterly wind from the South China Sea. A higher WHO-TEQ value of dioxin-like PCB (mainly attributed to the relatively higher WHO-TEQ value of PCB 126) in Yuen Long during winter, compared with other months, could also be related to the regional transport by the winter monsoon wind and the low mixing height in winter. Spatially, air concentrations of PCDD/F and dioxin-like PCB demonstrated a west-to-east gradient (with Yuen Long>Tsuen Wan>Tap Mun). It is suggested that PCDD/F and dioxin-like PCB were transported into the western airshed of Hong Kong from the Pearl River Delta by land-sea breeze circulation and confined to the northwestern part, due to the blocking effect of the northwestern airshed in Hong Kong.     

Characterization of organic matter in pristine and contaminated coastal marine sediments using solid-state 13C NMR, pyrolytic and thermochemolytic methods: a case study in the San Diego harbor area.

Chemical composition of coastal marine sedimentary organic matter (SDOM) is a function of natural and anthropogenic inputs to the system. In this study a combination of analytical techniques: 13C nuclear magnetic resonance (NMR), pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and tetramethylammonium hydroxide thermochemolysis-gas chromatography/mass spectrometry (TMAH thermochemolysis-GC/MS) were used to study the contribution of hydrophobic organic contaminants and terrestrial OM to the SDOM. Sediments were collected from two sites in the San Diego Bay: Paleta Creek, which is contaminated, and Coronado Cayes, which is relatively pristine. Concentrations of polycyclic aromatic hydrocarbons (PAHs) at both sites, as determined by ultrasonically assisted lipid extraction are found to be higher in the surface layer, to generally decrease with depth, and to be present at about two orders of magnitude higher concentration at the contaminated site as compared to the pristine site. The sediment samples were partially deashed with HF/HCI treatment before further analysis. 13C-NMR spectra of the Paleta Creek samples show a higher aromatic carbon content and a distinct phenolic carbon peak. This suggests a large input from terrestrial carbon (lignin). Data from both Py-GC/MS and TMAH thermochemolysis-GC/MS support this and indicate the presence of lignin-derived residues, primarily of the guaiacyl type at the contaminated site. In contrast, SDOM at the Coronado Cayes site exhibits less terrestrial input. In general, the SDOM resembles soil OM rather than typical marine SDOM. Chemical analyses of the lipid-extracted, partially deashed sediments, does not reveal the presence of any PAHs.     

Population dynamics of the acorn barnacles, Tetraclita squamosa and Tetraclita japonica (Cirripedia: Balanomorpha), in Hong Kong

Tetraclita squamosa and Tetraclita japonica are common, intertidal barnacles. In Hong Kong, the population dynamics of the two species exhibited spatial and temporal variation on two semi-exposed shores. T. squamosa produced egg masses from May–June and annual settlement and recruitment occurred from June–July. In contrast, settlement and recruitment of T. japonica was sparse from March–May, but intensified in July–October. Mature gonads and egg masses were, however, only present from September–November, suggesting the larvae from the two settlement pulses originated from other locations as well as Hong Kong populations. Settlement intensity and post-recruitment mortality of the two species varied between sites, possibly due to spatial variation in free rock space, physical transport of larvae and abundance of food in the water column.Communicated by T. Ikeda, Hakodate     

Interactions of organic compounds with wastewater dissolved organic matter: role of hydrophobic fractions

The role of structural fractions of dissolved organic matter (DOM) from wastewater in the sorption process of hydrophobic organic compounds is still not clear. In this study, DOM from two wastewater treatment plants (Lachish and Netanya, Israel) was fractionated to hydrophobic acid (HoA) and hydrophobic neutral (HoN) fractions. The fractions were characterized and their sorptive capabilities for s-triazine herbicides and polycyclic aromatic hydrocarbons (PAHs) were studied. For all sorbates, the binding to the HoN fractions was much higher than to HoA fractions. The HoA fractions were more polar than the HoN fractions, containing a higher level of carboxylic functionalities. However the higher binding coefficients of atrazine (2-chloro-4-ethylamine-6-isopropylamino-s-triazine) and ametryn [2-(ethylamino)-4-isopropylamino-6-methyl-thio-s-triazine] obtained for the HoN fractions suggest that their sorption is governed by hydrophobic-like interactions rather than H bonding. The values of binding coefficients of PAHs measured for the HoN fractions were within the range reported for humic acids and much higher than other fractions, suggesting that this fraction plays an important role in the overall sorption of these compounds by DOM. Higher sorption coefficients were measured for the Netanya DOM sample containing higher level of hydrophobic fractions (HoA + HoN) than the Lachish DOM, suggesting that the sorption of hydrophobic organic compounds by DOM is governed by the level of these structural substances. The evaluation of mobility of organic pollutants by wastewater irrigation requires not only assessment of the total carbon concentration but also, more importantly, the content of the hydrophobic fractions.     

Reproductive development of the barnacle Chthamalus malayensis in Hong Kong: implications for the life-history patterns of barnacles on seasonal, tropical shores

Hong Kong, lying just below the Tropic of Cancer (22°17′N, 114°09′E), experiences a strongly seasonal environment, with a cool almost temperate winter and a hot, tropical, summer. Histological sectioning of the gonads of the high-shore barnacle, Chthamalus malayensis Pilsbry, showed a seasonal trend in the development of its reproductive organs. Four stages of female gonad development were identified according to the cell types present: post-spawning, resting, growth and mature stages. The female gonad was mature from April to November, which was related to seawater temperatures, and entered a resting phase from December to March. Although the male gonad showed a seasonal developmental trend and reached maximum maturity in summer, the seminal vesicles were full of spermatozoa and functional throughout the year. The reproductive season of this species is therefore solely dependant upon the maturity of the female gonad. The estimated maximum number of broods per year was up to 10 and the maximum number of eggs produced per brood can reach 3,000 eggs. The minimum size for female gonad maturity was 6 mm rostro-carinal diameter (RCD) at which size, the barnacles were ~6-month old. Sperm production occurred at a smaller size (2 mm=2-month old). Compared with Chthamalus montagui and Chthamalus stellatus from temperate regions, C. malayensis produced a greater number of broods per year, had a longer reproductive period and faster gonad development. Chthamaloid barnacles in tropical regions may, therefore, invest more energy per year in reproduction during their life span. Contrary to the seasonal gonad developmental pattern of C. malayensis in the present study, however, C. malayensis in Singapore (which experiences only slight seasonal variation) had mature female and male gonads throughout the year, further supporting the strong role of climatic conditions effecting the reproductive biology of barnacles.     

Sorption-desorption behavior of polycyclic aromatic hydrocarbons in upstream and downstream river sediments

Sorption and desorption behaviors of phenanthrene and naphthalene were studied with the whole sediment, humic acid (HA) and humin samples from downstream and upstream sites along the Kishon River, Israel. The 13C nuclear magnetic resonance spectra and the sorption coefficients suggest that sorption occurs to both aromatic and aliphatic moieties of the sedimentary organic matter and that rigid paraffinic domains probably contribute to the sorption non-linearity. The carbon-normalized Freundlich affinity values for the two sorbates were significantly higher for the whole sediment and humin samples from the downstream region of the river than for the upstream sediment samples. On the basis of the measured affinity values, the sorbents can be arranged in the following order: humin>HA>whole sediment. Phenanthrene exhibited the lowest desorption from the whole sediment samples compared with the other sorbents. For naphthalene, the desorption hysteresis obtained with the whole sediment and humin samples were similar: both exhibited a decrease in desorption with decreasing solute concentration. The higher sorption affinities observed for all the organic fractions from the downstream sediment are suggested to be related to the low levels of polar domains and humin content. It is concluded that in bulk sediment samples, the overall contribution of the HA fraction to short-term sorption is of high importance, but the sorption non-linearity is controlled mainly by the humin complexes. The low desorption potential recorded for the whole sediment samples could affect the natural attenuation of the sorbed hydrophobic organic compounds.     

Nitrogen Oxide Flux from an Agricultural Soil During Winter Fallow in the Upper Coastal Plain of North Carolina,U.S.A.

Abstract

Incorporation of the remaining crop residue, including the root system, of grain (soybean and corn) and fiber (cotton) crops into the soil following harvest is a common agricultural practice. The crop residue represents a substantial portion of nitrogen initially applied as fertilizer, and thus is a potential source of nitrogen for NO emissions during the winter fallow period. Fluxes of NO and NO₂ were measured from fallow fields from February 7 to March 23, 1994, using a dynamic chamber technique (ambient air as the carrier gas). Average NO flux rates, as a function of previous crop residue, were 9.2 (range –4.2 to 76) ng–N m^–2 s^–1 for soybean, 6.1 (range –11.7 to 110) ng–N m^–2 s^–1 for cotton, and 4.7 (range –0.2 to 40) ng–N m^–2 s^–1 for corn. Maximum NO fluxes were observed in mid–morning when soil temperatures were lowest. Minimum NO flux occurred after mid–afternoon when soil temperature reached a maximum. The decrease in NO flux with increase in soil temperature (5 cm depth) reflected the existence of a NO compensation concentration (i.e., the rate for the NO consumption reactions continued to increase with increase in temperature). NO₂ deposition was calculated for 92% of the data points, with no trend in deposition between the three fields and their corresponding crop residue. These results indicate that significant fluxes of NO are generated from fallow agricultural fields following incorporation of the residue from the previous crop.     

Adaptations to barnacle fouling in the mangroves <Emphasis Type="Italic">Kandelia obovata</Emphasis> and <Emphasis Type="Italic">Aegiceras corniculatum</Emphasis>

Mangrove trees planted for restoration or rehabilitation often fail to show satisfactory survivals. Although it is generally assumed that barnacle fouling is a factor in mangrove mortality, the sub-lethal response of mangroves to this fouling is not known. In the present study, we compare the leaf morphology (stomata density, leaf thickness, percentage thickness of palisade layer and number of hypodermal layers), lenticel density and the plant fitness (number of flowers or droppers per tree) between mangroves fouled by the acorn barnacle Fistulobalanus albicostatus (the fouled group, number of barnacles ~ 120 individuals per tree) and non-fouled mangroves (the control group). We observed 55 Kandelia obovata from three locations, two in Hong Kong (n = 35, fouled 25 and control 10) and one location in Taiwan (n = 20, fouled 10 and control 10). Aegiceras corniculatum (n = 45) was observed from two sites in Hong Kong, one on the east coast (n = 20, 10/10) and one on the west coast (n = 25, 10/15). In seedlings (K. obovata n = 10, 5/5), fouling density did not affect leaf morphology. In mature trees, however, leaves from fouled trees had significantly higher density of stomata and stem lenticel, a lower percentage thickness of leaf palisade layer and more layers of lower hypodermis in the leaves, probably for compensating the impeded gaseous exchange functions of the lenticels. The number of droppers and flowers on fouled mangroves was significantly lower. It is possible that after compensating for respiratory stress, the plant had less energy available for reproduction. Although there was no obvious barnacle-induced mortality in this study, barnacles appear to be related to a reduction in plant fitness. This may induce sufficient stress that over time fouled mangroves cannot sustain viable populations.     

Effect of epibiosis on the fitness of the sandy shore snail<Emphasis Type="Italic"> Batillaria zonalis</Emphasis> in Hong Kong

Batillaria zonalis is a common snail on Hong Kong sandy shores, occupying the low-mid shore. Shells of B. zonalis (basibiont) are often fouled with the rock oyster Saccostrea cucullata and the barnacle Balanus reticulatus (epibiont). This epibiotic interaction has a negative impact on the fitness of B. zonalis in terms of impairing fecundity, mobility and metabolism of fouled individuals. During the reproductive season, fouled snails had lower Gonadosomatic Index and fewer egg-bearing individuals than non-fouled snails. Fouled snails crawled in a more tortuous pathway and with lower speed when compared with non-fouled snails. Reduction in oxygen consumption and metabolic rate in fouled snails further suggested the restriction in mobility of B. zonalis by the epibionts. Glycogen content in the foot muscle tissues and hepatopancreas of fouled and non-fouled snails was, however, similar, revealing epibiosis does not influence the energy storage of B. zonalis. Mortality of fouled and non-fouled snails was similar under laboratory conditions, suggesting epibiosis does not influence the survivorship of B. zonalis in Hong Kong. Impairment in the fitness of fouled B. zonalis indicates that epibiosis can influence the population dynamics of B. zonalis in Hong Kong.Communicated by T. Ikeda, Hakodate