Ozonation catalyzed by homogeneous and heterogeneous catalysts for degradation of DEHP in aqueous phase

Di-(2-ethyl hexyl) phthalate (DEHP), a recalcitrant and an endocrine disrupting chemical, was studied for its removal from wastewater by advanced oxidation process. The effects of pH, transition metal ions, and granular activated carbon (GAC) were investigated. Removal of DEHP increased with increase in pH and among metal ions Cr(III) was found to be the most active catalyst to remove DEHP. In the case of GAC, original carbon (G0) and GAC pre-ozonated in gas phase for 10 min (G10) were tested as catalysts in catalytic ozonation and found G0 to be more active than G10. This is because, during pre-ozonation, basic groups like chromene, pyrones and also graphene layers were oxidized to acidic surface oxygen groups. These basic surface groups are reported to be active catalytic centres for ozone decomposition into .OH which is a strong oxidant. According to kinetic manipulations, DEHP degradation rate constant due to .OH was affected by the catalyst while that due to direct ozonation is same in all cases with or without catalyst. G0 was doped with chromia gels (G0/CrA) to combine the benefits of homogeneous and heterogeneous catalysis. G0/CrA showed lower catalytic efficiency than that of only G0. This might be because of changes in surface structure of GAC caused by doping of chromia gel and changes in chemical nature of Cr(III) during formation of gel. A good correlation was found between the rate constants of ozone decay and DEHP degradation (R2=0.96). This correlation confirms that ozone decomposition into .OH is a critical factor for the activity of a catalyst during ozonation.     

Seasonal variations of monoterpene emissions from Pinus densiflora in East Asia

The emission rates and compositions of monoterpene from Pinus densiflora were investigated in the Gumsung (GM) and Worak (WM) mountains. The standard emission rates (ERs: ERs is the monoterpene emission rate at standard temperature, 30 degrees C) from P. densiflora ranged from 0.817 to 1.704 (mugC/gdw-h). The ERs and beta-values of total monoterpene were measured at the two study sites (GM and WM). In the spring and summer, the ERs were the highest, while relatively low values (<0.058mugC/gdw-h) were measured in the autumn and winter. In GM and WM sites the beta-value obtained for the different seasons ranged from 0.047 to 0.179, with an average of 0.09. The major monoterpene compounds from P. densiflora were alpha-pinene, myrcene, beta-phellandrene, d-limonene and alpha-terpinene. The fractional compositions of individual monoterpene compounds were significantly different between the two test sites in the summer and winter. The ERs of the older group (31-40 years) were higher than those in the younger group (21-30 years). However, the monoterpene compositions were similar between the two age groups.     

Estimating naphthenic acids concentrations in laboratory-exposed fish and in fish from the wild

Naphthenic acids (NAs) are the most water-soluble organic components found in the Athabasca oil sands in Alberta, Canada, and these acids are released into aqueous tailing waters as a result of bitumen extraction. Although the toxicity of NAs to fish is well known, there has been no method available to estimate NAs concentrations in fish. This paper describes a newly developed analytical method using single ion monitoring gas chromatography-mass spectrometry (GC-MS) to measure NAs in fish, down to concentrations of approximately 0.1mgkg(-1) of fish flesh. This method was used to measure the uptake and depuration of commercial NAs in laboratory experiments. Exposure of rainbow trout (Oncorhynchus mykiss) to 3mg NAsl(-1) for 9d gave a bioconcentration factor of approximately 2 at pH 8.2. Within 1d after the fish were transferred to NAs-free water, about 95% of the NAs were depurated. In addition, the analytical method was used to determine if NAs were present in four species of wild fish - northern pike (Esox lucius), lake whitefish (Coregonus clupeaformis), white sucker (Catostomus commersoni), walleye (Sander vitreus) - collected from near the oil sands. Flesh samples from 23 wild fish were analyzed, and 18 of these had no detectable NAs. Four fish (one of each species) contained NAs at concentrations from 0.2 to 2.8mgkg(-1). The GC-MS results from one wild fish presented a unique problem. However, with additional work it was concluded that the NAs concentration in this fish was <0.1mgkg(-1).     

Effectiveness of compacted soil liner as a gas barrier layer in the landfill final cover system

A compacted soil liner (CSL) has been widely used as a single barrier layer or a part of composite barrier layer in the landfill final cover system to prevent water infiltration into solid wastes for its acceptable hydraulic permeability. This study was conducted to test whether the CSL was also effective in prohibiting landfill gas emissions. For this purpose, three different compaction methods (i.e., reduced, standard, and modified Proctor methods) were used to prepare the soil specimens, with nitrogen as gas, and with water and heptane as liquid permeants. Measured gas permeability ranged from 2.03x10(-10) to 4.96x10(-9)cm(2), which was a magnitude of two or three orders greater than hydraulic permeability (9.60x10(-13) to 1.05x10(-11)cm(2)). The difference between gas and hydraulic permeabilities can be explained by gas slippage, which makes gas more permeable, and by soil-water interaction, which impedes water flow and then makes water less permeable. This explanation was also supported by the result that a liquid permeability measured with heptane as a non-polar liquid was similar to the intrinsic gas permeability. The data demonstrate that hydraulic requirement for the CSL is not enough to control the gas emissions from a landfill.     

环境基质中药物残留的固相提取与分析

废水流出物常常不可避免地进入地表水和用于饮用水资源的含水层．因废水再循环常常进入饮用水层,各种废水中的污染物最终会污染饮用水．以往环保部门一直比较注重农药和工业污染物,但最近的研究发现:废水流出物中的某些药物残留已达到了相当令人关注(１μｇ·１－１即ｐｐｂ)的程度．传统的分析技术(如液液萃取和ＧＣ/ＭＳ) 对极性较弱的化合物(ＰＣＢｓ和许多农药)比较有效,但对于极性相对较强的药物污染物而言,固相提取(ＳＰＥ)与ＬＣ/ＭＳ技术更适合于样品提取分析。     

A Critique of the Recovery of Greenback Cutthroat Trout

Abstract: There are no examples of recovery of fish listed under the U.S. Endangered Species Act, but the number of federally threatened greenback cutthroat trout (  Oncorhynchus clarki stomias ) populations is approaching the delisting goal. We evaluated recovery of this subspecies in light of developing theory in conservation biology and with regard to recovery of other salmonids in the inland western United States. Four of the five criteria used to define populations that would count toward delisting appeared to underestimate the risk of extinction of those populations. Typically, recovery goals for numbers of greenback cutthroat trout populations were less stringent than those for other inland salmonids petitioned for listing or listed as threatened under the Endangered Species Act and were comparable to those for a federally endangered species. Before delisting is considered, we propose that historical populations be replicated in additional waters to protect genetic diversity and that existing populations be enlarged to reduce their vulnerability to demographic variation, to increase their access to refugia, and to permit reestablishment of mobile life histories. Existing stocks should also be evaluated to determine whether they represent distinct population segments.     

Behaviour of echinoid larvae around sharp haloclines: effects of the salinity gradient and dietary conditioning

We examined larval response to a range of sharp haloclines and determined the effect of dietary conditioning on that response in the sea urchins Echinometra lucunter and Arbacia punctulata. We reared larvae in the laboratory under a high or low concentration of either single (Isochrysis galbana) or mixed (Isochrysis galbana, Dunaliella tertiolecta, Thalassiosira weissflogii) microalgal species. For both species of sea urchins, rate of larval development was faster and age-specific larval length and width were greater in high-ration than low-ration diets. We examined the distribution of two- and four-arm larvae of E. lucunter from each diet treatment and of four-arm larvae of A. punctulata from the high-ration diets in cylinders with experimentally constructed haloclines. In three of the halocline treatments, the salinity of the bottom layer was 33‰ and that of the top layer was 21, 24 or 27‰ (21/33, 24/33 and 27/33) and in a fourth one, the salinities of the bottom and top layer were 30 and 21‰, respectively (21/30). The position of larvae in the cylinders varied with the steepness of the halocline and with dietary conditioning for both sea urchin species and all developmental stages tested. Significantly more larvae crossed the haloclines into water of 24 and 27‰ salinity than into water of 21‰ salinity. We observed an effect of diet on the position of larvae in the cylinders, and that effect varied among halocline treatments for both species. The proportion of larvae of E.lucunter that crossed the halocline was greater in low- than high-ration diets in the 24/33 and 27/33 treatments. Position of four-arm larvae in the cylinders also varied with food quality in high-ration diets: for E.lucunter in the 24/33 treatments, and for A. punctulata in the 21/30 treatments, more larvae from the single- than from the mixed-species diets were present above the halocline. Salinity in the adult habitat during most of the active reproductive period ranged from 15 to 40‰. We showed that larvae can respond to gradients in salinity, and therefore can remain within a water mass of higher salinity overlying the adult habitat. However, survival of poorly fed larvae may be increased if they are introduced into a new water mass and carried away from a nutritionally poor environment. Received: 9 July 1997 / Accepted: 12 January 1998     

Reproductive endocrine disruption in smallmouth bass (Micropterus dolomieu) in the Potomac River basin: spatial and temporal comparisons of biological effects

A high prevalence of intersex or testicular oocytes (TO) in male smallmouth bass within the Potomac River drainage has raised concerns as to the health of the river. Studies were conducted to document biomarker responses both temporally and spatially to better understand the influence of normal physiological cycles, as well as water quality and land-use influences. Smallmouth bass were collected over a 2-year period from three tributaries of the Potomac River: the Shenandoah River, the South Branch Potomac and Conococheague Creek, and an out-of-basin reference site on the Gauley River. The prevalence of TO varied seasonally with the lowest prevalence observed in July, post-spawn. Reproductive maturity and/or lack of spawning the previous spring, as well as land-use practices such as application of manure and pesticides, may influence the seasonal observations. Annual, seasonal, and site differences were also observed in the percentage of males with measurable concentrations of plasma vitellogenin, mean concentration of plasma vitellogenin in females, and plasma concentrations of 17β-estradiol and testosterone in both sexes. Bass collected in the South Branch Potomac (moderate to high prevalence of TO) had less sperm per testes mass with a lower percentage of those sperm being motile when compared to those from the Gauley River (low prevalence of TO). An inverse relationship was noted between TO severity and sperm motility. An association between TO severity and wastewater treatment plant flow, percent of agriculture, total number of animal feeding operations, the number of poultry houses, and animal density within the catchment was observed.     

Hydrology, suspended sediment dynamics and nutrient loading in Lake Takkobu, a degrading lake ecosystem in Kushiro Mire, northern Japan

Suspended sediment and nutrient loadings from agricultural watersheds have lead to habitat degradation in Lake Takkobu. To examine their relationships with land-use activities, we monitored sediment, nutrient and water discharges into the lake for a 1-year sampling period. The Takkobu River contributed the largest portion of the annual water discharge into the lake, compared with the other tributaries. During dry conditions, lake water flowed into the Kushiro River, and conversely during flooding, Kushiro River water flowed into the lake. Inflows from the Kushiro River had a high proportion of inorganic matter, with high concentrations of total nitrogen and total phosphorus, attributed to agricultural land-use development and stream channelization practiced since the 1960s in the Kushiro Mire. Nutrient loadings from these two rivers were significantly higher during flooding than in dry conditions. However, there was no clear correlation between river discharge and nutrient concentrations. Since land-use activities in the Kushiro River and Takkobu River watersheds were concentrated near rivers, nutrients easily entered the drainage system under low flow conditions. In contrast, water discharged from small, forest-dominated watersheds contained a low proportion of inorganic matter, and low nutrient concentrations. The suspended sediment delivered to the lake during the sample period was estimated as approximately 607 tons, while the total nitrogen and total phosphorus inflows were about 10,466 and 1,433 kg, respectively. Suspended sediment input into the lake was 65%, and total nitrogen and total phosphorus were 40% and 48%, respectively, being delivered by the Kushiro River.