Residues of endosulfan and other selected organochlorine pesticides in farm areas of the Lower Fraser Valley, British Columbia, Canada

Crop soils, ditch sediments, and water flowing from several farm areas to salmon tributary streams of the Fraser River in the Lower Fraser Valley (LFV) of British Columbia, Canada, were sampled in 2002-2003 to quantify for residues of an organochlorine cyclodiene pesticide, endosulfan (END = alpha-endosulfan + beta-endosulfan + endosulfan sulfate). Residues from historical use of other selected organochlorine pesticides, namely, cyclodienes (aldrin, alpha-chlordane, gamma-chlordane, dieldrin, endrin, endrin aldehyde, heptachlor, and heptachlor epoxide), hexachlorocyclohexanes [alpha-benzene-hexachloride (alpha-BHC), beta-BHC, delta-BHC, and gamma-BHC (lindane)], and DDT-related compounds (p,p-DDT, p,p-DDD, p,p-DDE, and methoxychlor) were also determined. Reference and background levels of these pesticides in ditches leading to fish streams were obtained from pristine watershed areas. Varying amounts of END residues were detected in soils (<0.02-5.60 mg kg(-1) dry wt.) and ditch sediments (<0.02-3.33 mg kg(-1) dry wt.) in mainly three of five farm areas sampled. Likewise, residues (excluding END) of other selected organochlorine compounds such as aldrin, BHC, chlordane, endrin, p,p-DDT, methoxychlor, and their respective major transformation products (endosulfan sulfate, dieldrin, endrin aldehyde, heptachlor, heptachlor epoxide, p,p-DDD, and p,p-DDE) were found in crop soils (<0.02-16.2 mg kg(-1) dry wt.) and sediments (<0.02-9.73 mg kg(-1) dry wt.). Most of these pesticides (END: <0.01-1.86 microg L(-1); other selected organochlorine pesticides: <0.0.1-1.50 microg L(-1)) were also found in ditch water leading to salmon streams in several farms. The END levels of crop soils from the same LFV study farms in 1994 and 2003 indicated an estimated decline of 22% to 1.35 mg kg(-1) dry wt. during that period. This reduction was probably due to the increasing use of alternate pesticides (e.g., organophosphorus compounds). Some possible biological implications of these pesticide residues on nontarget organisms in the LFV are discussed.     

Bird species migration ratio in East Asia, Australia, and surrounding islands

Bird migration and its relationship with the contemporary environment have attracted long-term discussion. We calculated the avian migration ratio (the proportion of breeding species that migrate) in the areas from 70°E to 180°E and examined its relationship with the annual ranges of ambient temperature, primary productivity (estimated by the Enhanced Vegetation Index), and precipitation, along with island isolation and elevational range. The avian migration ratio increased with increasing latitude in general but varied greatly between the two hemispheres. Additionally, it showed minimal differences between continents and islands. Our analyses revealed that the seasonality of ambient temperature, which represents the energy expenditure of birds, is the dominant factor in determining bird species migration. Seasonality in primary productivity and other environmental factors play an indirect or limited role in bird species migration. The lower avian migration ratio in the Southern Hemisphere can be attributed to its paleogeographical isolation, stable paleoclimate, and warm contemporary environment. Under current trends of global warming, our findings should lead to further studies of the impact of warming on bird migration.     

Combustion-derived substances in deep basins of Puget Sound: historical inputs from fossil fuel and biomass combustion

Reconstructions of 250 years historical inputs of two distinct types of black carbon (soot/graphitic black carbon (GBC) and char-BC) were conducted on sediment cores from two basins of the Puget Sound, WA. Signatures of polycyclic aromatic hydrocarbons (PAHs) were also used to support the historical reconstructions of BC to this system. Down-core maxima in GBC and combustion-derived PAHs occurred in the 1940s in the cores from the Puget Sound Main Basin, whereas in Hood Canal such peak was observed in the 1970s, showing basin-specific differences in inputs of combustion byproducts. This system showed relatively higher inputs from softwood combustion than the northeastern U.S. The historical variations in char-BC concentrations were consistent with shifts in climate indices, suggesting an influence of climate oscillations on wildfire events. Environmental loading of combustion byproducts thus appears as a complex function of urbanization, fuel usage, combustion technology, environmental policies, and climate conditions.     

Fate of polycyclic aromatic hydrocarbons during vitrification of incinerator ash in a coke bed furnace

Fate of polycyclic aromatic hydrocarbons (PAHs) during the vitrification of fly ash and bottom ash from the municipal waste incinerator in a coke bed furnace was investigated. In this system, both coke and lime were added to enhance the melting reaction. The major PAH sources in this system were ash and coke, which respectively contributed 97% and 3% of PAHs in the input-mass. During vitrification process, low molecular PAHs (LM-PAH, 2-3-ring), median molecular PAHs (MM-PAH, 4-ring) and high molecular PAHs (HM-PAH, 5-7-ring) mass respectively accounted for >99%, >99% and 84% of the output-mass emitted as the stack flue gas; while those discharged from the slag were <1%, <1% and 16%, respectively. The O/I (output-mass/input-mass) ratio of LM-, MM- and HM-PAHs were 0.063, 0.002 and <0.001, respectively. The high distribution in flue gas and O/I ratio of LM-PAHs is reasonable since they are more easily evaporated, hence difficult to be removed by air pollution control devices. On the contrary, the HM-PAHs, having lower vapor pressure, primarily stays mainly in slag. Based on the 21 total PAH content in feeding ash and slag, the reduction efficiency of the coke bed furnace was >99.9%. To minimize the risk of secondary pollution, the efficiency of coke bed furnace should be improved to reduce the PAH emission into ambient air.     

The effects and the toxicity increases caused by bicarbonate,chloride, and other water components during the UV/TiO<Subscript>2</Subscript> degradation of oxazaphosphorine drugs

The influences of HCO₃ ^?, Cl^?, and other components on the UV/TiO₂ degradation of the antineoplastic agents ifosfamide (IFO) and cyclophosphamide (CP) were studied in this work. The results indicated that the presence of HCO₃ ^?, Cl^?, NO₃ ^?, and SO₄ ^2? in water bodies resulted in lower degradation efficiencies. The half-lives of IFO and CP were 1.2 and 1.1 min and increased 2.3–7.3 and 3.2–6.3 times, respectively, in the presence of the four anions (initial compound concentration = 100 μg/L, TiO₂ loading =100 mg/L, anion concentration = 1000 mg/L, and pH = 8). Although the presence of HCO₃ ^? in the UV/TiO₂/HCO₃ ^? system resulted in a lower degradation rate and less byproduct formation for IFO and CP, two newly identified byproducts, P11 (M.W. = 197) and P12 (M.W. = 101), were formed and detected, suggesting that additional pathways occurred during the reaction of ?CO₃ ^? in the system. The results also showed that ?CO₃ ^? likely induces a preferred ketonization pathway. Besides the inorganic anions HCO₃ ^?, Cl^?, NO₃ ^?, and SO₄ ^2?, the existence of dissolved organic matter in the water has a significant effect and inhibits CP degradation. Toxicity tests showed that higher toxicity occurred in the presence of HCO₃ ^? or Cl^? during UV/TiO₂ treatment and within 6 h of reaction time, implying that the effects of these two anions should not be ignored when photocatalytic treatment is applied to treat real wastewater.     

Biodegradation of coplanar polychlorinated biphenyls by anaerobic microorganisms from estuarine sediments.

In this study, we investigated the biodegradability of biphenyl and 5 congeners (one non-planar and four coplanar) of polychlorinated biphenyl (PCB). Biphenyl, the non-planar congener 2,3',4',5-tetrachlorobiphenyl (25-34 CB), and the four coplanar congeners 3,3',4,4'-tetrachlorobiphenyl (34-34 CB), 3,4,4',5-tetrachlorobiphenyl (345-4 CB), 3,3',4,4',5-pentachlorobiphenyl (345-34 CB), and 3,3',4,4',5,5'-hexachlorobiphenyl (345-345 CB) were amended at a concentration of 10 mg/L into anoxic sediment slurries collected from the estuaries of the Tansui River and the Erjen River. During 2 years' incubation under sulfidogenic conditions, biphenyl was persistent, while all other chlorinated congeners, except for 345-345 CB, were dechlorinated with or without a lag period in sediment slurries collected from both rivers. Dechlorination of coplanar and non-planar congeners began with para chlorine removal. All para chlorines from the mono-, di-, and trichlorobiphenyl groups could be removed by sediment slurries from both rivers. Microbial communities in sediment from the Erjen River additionally fostered meta-dechlorination activity, but only after removal of all the para chlorines. Addition of Tween 20 (0.05%, v/v) into sediment slurries from the Tansui River did not enhance dechlorination rates or extents, but the addition of toluene- or 3-chlorobenzoate-adapted sediments enhanced dechlorination of 34-34 CB and 345-4 CB.     

Characteristics of springtime profiles and sources of ozone in the low troposphere over northern Taiwan

To quantify the possible sources of the high ambient ozone concentration in the low troposphere over Taiwan, ozone sounding data from a two-year intensive field measurement program conducted in April and early May of 2004 and 2005 in northern Taiwan has been examined. We found that the vertical ozone distributions and occurrence of enhanced ozone in the lower troposphere (below 6 km) mainly resulted from (1)Type NE: the long-range transport of ozone controlled by the prevailing northeasterly winds below 2 km, (2)Type LO: the local photochemical ozone production process, and (3)Type SW: the strong southwest/westerly winds aloft (2–6 km). In the boundary layer (BL), where Asian continental outflow prevails, the average profile for type NE is characterized by a peak ozone concentration of nearly 65 ppb at about 1500 m altitude. For type LO, high ozone concentration with an average ozone concentration greater than 80 ppb was also found in the BL in the case of stagnant atmospheric and sunny weather conditions dominated. For type SW, significant ozone enhancement with average ozone concentration of 70–85 ppb was found at around 4 km altitude. It is about 10 ppb greater than that of the types NE and LO at the same troposphere layer owing to the contribution of the biomass burning over Indochina. Due to Taiwan's unique geographic location, the complex interaction of these ozone features in the BL and aloft, especially features associated with northeasterly and south/southwesterly winds, have resulted in complex characteristics of ozone distributions in the lower troposphere over northern Taiwan.     

Decomposition of perfluorocarboxylic acids (PFCAs) by heterogeneous photocatalysis in acidic aqueous medium

Decomposition of perfluorocarboxylic acids (PFCAs) is of prime importance since they are recognized as persistent organic pollutants and are widespread in the environment. PFCAs with longer carbon chain length are particularly of interest because of their noted recalcitrance, toxicity, and bioaccumulation. Here in this study, we demonstrate efficient decomposition of three important PFCAs such as perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) by heterogeneous photocatalysis with TiO₂ as a photocatalyst in acidic aqueous solutions. The PFCAs were decomposed into shorter carbon chain length PFCAs and fluoride ions. Photoholes of excited TiO₂ generated upon UV-irradiation are found to be the oxidation sites for PFCAs. Therefore, creation and sustenance of these photoholes in the acidic aqueous medium has enhanced the decomposition of PFCAs. Heterogeneous photocatalytic treatment achieved more than 99% decomposition and 38% complete mineralization of PFOA in 7 h. The decomposition of other PFCAs was as high as 99% with a defluorination efficiency of 38% for PFDA and 54% for PFNA. The presence of perchloric acid was found to enhance the decomposition by facilitating the ionization of PFCAs. The oxygen present in the medium served both as an oxidant and an electron acceptor. The mechanistic details of PFCA decomposition and their corresponding mineralization are elaborated.     

Determination of estrogenic compounds in wastewater using liquid chromatography-tandem mass spectrometry with electrospray and atmospheric pressure photoionization following desalting extraction

Two complementary LC-MS ionization methods, electrospray (ESI) and atmospheric pressure photoionization (APPI), have been optimized to determine three natural estrogenic compounds (estrone, 17beta-estradiol and estriol) and two synthetic estrogenic compounds (17alpha-ethynylestradiol and diethylstilbestrol) in the influent and effluent of wastewater treatment plants (WWTPs). The wastewater samples were first subjected to solid-phase extraction coupled with desalting extraction to remove matrix interference. The analytes were then detected using liquid chromatography-tandem mass spectrometry (LC-MS-MS) with ESI and dopant-assisted (DA) APPI to evaluate the ion suppression effect and to complement the detection and quantification of estrogenic compounds in complex wastewater samples. The average ion suppression factors for the extracts of the WWTP influent analyzed using ESI and APPI were 52+/-5% and 27+/-7%, respectively. The sensitivity and ionization efficiency of the LC-ESI-MS-MS system decreased dramatically when a complex matrix was present in the WWTP influent sample. Estrogenic compounds could be detected in the WWTP influent and effluent samples at concentrations below the parts-per-billion level. The lower detection limits obtained when using ESI and the higher matrix tolerance of the APPI method allowed the complete quantification of estrogenic compounds in very complex samples in a complementary manner.