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.     

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.     

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.     

Estimation of phosphorus flux in rivers during flooding

Reservoirs in Taiwan are inundated with nutrients that result in algal growth, and thus also reservoir eutrophication. Controlling the phosphorus load has always been the most crucial issue for maintaining reservoir water quality. Numerous agricultural activities, especially the production of tea in riparian areas, are conducted in watersheds in Taiwan. Nutrients from such activities, including phosphorus, are typically flushed into rivers during flooding, when over 90 % of the yearly total amount of phosphorous enters reservoirs. Excessive or enhanced soil erosion from rainstorms can dramatically increase the river sediment load and the amount of particulate phosphorus flushed into rivers. When flow rates are high, particulate phosphorus is the dominant form of phosphorus, but sediment and discharge measurements are difficult during flooding, which makes estimating phosphorus flux in rivers difficult. This study determines total amounts of phosphorus transport by measuring flood discharge and phosphorous levels during flooding. Changes in particulate phosphorus, dissolved phosphorus, and their adsorption behavior during a 24-h period are analyzed owing to the fact that the time for particulate phosphorus adsorption and desorption approaching equilibrium is about 16 h. Erosion of the reservoir watershed was caused by adsorption and desorption of suspended solids in the river, a process which can be summarily described using the Lagmuir isotherm. A method for estimating the phosphorus flux in the Daiyujay Creek during Typhoon Bilis in 2006 is presented in this study. Both sediment and phosphorus are affected by the drastic discharge during flooding. Water quality data were collected during two flood events, flood in June 9, 2006 and Typhoon Bilis, to show the concentrations of suspended solids and total phosphorus during floods are much higher than normal stages. Therefore, the drastic changes of total phosphorus, particulate phosphorus, and dissolved phosphorus in rivers during flooding should be monitored to evaluate the loading of phosphorus more precisely. The results show that monitoring and controlling phosphorus transport during flooding can help prevent the eutrophication of a reservoir.     

基于蒙特卡洛模拟与PMF模型的黄河流域沉积物重金属污染评价及源解析

沉积物是河流的重要组成部分,而沉积物中重金属的富集严重威胁着水环境安全.黄河流域沿程分布着众多工业城市,且流域水土流失量大,泥沙携带重金属进入河流导致沉积物重金属污染问题日趋严重,研究黄河流域沉积物中重金属污染状况对流域生态安全具有重要意义.收集2000~2020年发表的关于黄河流域沉积物中重金属（铅、镉、铬、砷、锌、铜、镍和汞）含量的数据,首先基于描述性统计及地统计法分析重金属的空间分布特征,进一步采用蒙特卡洛法进行地累积指数（I_geo）、潜在生态风险及毒性单位概率的评价,最后结合正定矩阵因子分解模型（PMF）与Pearson相关性分析确定污染源个数及贡献率.结果发现,黄河流域沉积物中ω（Pb）、ω（As）、ω（Zn）、ω（Ni）、ω（Cu）、ω（Hg）、ω（Cr）和ω（Cd）的均值分别为26.92、11.78、87.17、31.13、24.96、0.07、73.36和0.58 mg·kg^-1,分别超过黄河流域各省土壤背景值均值1.27、1.08、1.26、1.05、1.09、2.32、1.14和5.95倍,其中Cd超标倍数最大,应当引起重视;I_geo：Cd>Hg>Cr>Cu>Pb>Zn>As>Ni,Cd和Hg存在中度-严重污染;数据表明黄河流域上、中和下游沉积物重度生态风险占比分别为18.6%、15.7%和7.1%,呈递减趋势;黄河流域沉积物中重金属处于低毒性状态;溯源分析表明黄河流域沉积物重金属的4个来源分别是矿业源（42.2%）、自然活动（38.3%）、农业活动（11.6%）和电镀废水（7.9%）.研究结果可为黄河流域制定相关污染防控措施提供依据.     

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.     

Agricultural pesticide residues of farm runoff in the Okanagan Valley, British Columbia, Canada

The objectives of this study were to determine environmental occurrence and concentrations of selected currently-used-pesticides and some transformation products in agricultural farms in the Okanagan Valley (OKV), and to conduct a simple risk assessment of environmental pesticides levels detected in OKV on non-target aquatic organisms. The OKV is the tree fruit country of the Province of British Columbia where considerable amount of pesticides are applied annually. Water, sediment and soil samples were collected at eleven sites in early June and late September following rainfall events and/or extended periods of irrigation from drainage ditches and/or from small streams. Undisturbed reference sites were also sampled. Study results showed that forty of the eighty chemicals analyzed, including organochlorine, nitrogen-containing and organophosphate pesticides commonly used for OKV crops, were detected in runoff and small stream water samples. Among which, endosulfan-sulfate was the most frequently detected chemical. Also, azinophos-methyl (0.699-25.5 ng/L), diazinon (0.088-214 ng/L) exceeded, and α-, β- endosulfan, endosulfan sulphate approached the guidelines for the protection of aquatic life.     

Decomposition of perfluorooctanoic acid by microwaveactivated persulfate: Effects of temperature, pH, and chloride ions

Microwave-hydrothermal treatment of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in water with persulfate (S₂O ₈ ^2? ) has been found effective. However, applications of this process to effectively remediate PFOA pollution require a better understanding on free-radical scavenging reactions that also take place. The objectives of this study were to investigate the effects of pH (pH = 2.5, 6.6, 8.8, and 10.5), chloride concentrations (0.01?C0.15 mol·L^?1), and temperature (60°C, 90°C, and 130°C) on persulfate oxidation of PFOA under microwave irradiation. Maximum PFOA degradation occurred at pH 2.5, while little or no degradation at pH 10.5. Lowering system pH resulted in an increase in PFOA degradation rate. Both high pH and chloride concentrations would result in more scavenging of sulfate free radicals and slow down PFOA degradation. When chloride concentrations were less than 0.04 mol·L^?1 at 90°C and 0.06 mol·L^?1 at 60°C, presence of chloride ions had insignificant impacts on PFOA degradation. However, beyond these concentration levels, PFOA degradation rates reduced significantly with an increase in chloride concentrations, especially under the higher temperature.