Occurrence of diclofenac and selected metabolites in sewage effluents

Many pharmaceuticals along with their metabolites have been detected in environmental water samples in the recent decades. The analgesic diclofenac is widely used and thus enters the aquatic environment. Already at realistic environmental concentration levels harmful effects to different organisms have been demonstrated. As this could also be expected for its metabolites, their fate was examined. Six wastewater treatment plant effluents collected throughout Germany were analyzed for the drug and two of its hydroxylated metabolites, 4'-hydroxy diclofenac (4'-OHD) and 5-hydroxy diclofenac (5-OHD), together with the lactam of 4'-OHD, 4'-hydroxy diclofenac dehydrate (4'-OHDD). A quantitative analytical method has been developed using solid-phase extraction followed by LC-ESI-MS/MS. The limits of quantitation (LOQ) in sewage effluent were 0.06 mug/l for diclofenac and its hydroxyl metabolites and 0.07 microg/l for 4'-OHDD. Recoveries ranged from 62 to 81%. The metabolites were detected in the samples in median concentration ranges of 相似文献   

Fish tissue quality in the lower Mississippi River and health risks from fish consumption

Between 1990 and 1994, samples of three shellfish species (i.e. blue crab, Callinectes sapidus;crayfish, Procambarus acutis; and river shrimp, Macrobrachium ohionii) and 16 fish species and were collected at six sites along the lower Mississippi River by the Louisiana Department of Environmental Quality, Office of Water Resources in coordination with the US Environmental Protection Agency. The fish species included: bigmouth buffalo (Ictiobus cyanellus); blue catfish (Ictalurus furcatus); carp (Cyprinus carpio); channel catfish (Ictalurus punctatus); cobia (Rachycentron canadum); flathead catfish (Pylodictis olivaris); freshwater drum (Aplodinotus grunniens); largemouth bass (Micropterus salmoides); long nose gar (Lepisosteus osseus); red drum (Sciaenops ocellatus); red snapper (Lutjanus campechanus); smallmouth buffalo (Ictiobus bubalus); spotted gar (Lepisosteus oculatus); striped bass (Morone saxatilis); white bass (Morone chrysops); and white crappie (Pomoxis annularis). Organic compound and heavy metal concentrations were measured in 161 composite fish tissue samples where each composite included three to 10 individual fish. Nineteen chemicals, found at measurable levels in sample tissues, were used in calculations of lifetime excess cancer and non-cancer risks due to fish consumption. We calculated: 574 chemical-specific cancer risks; 41 total cancer risks; and 697 margins of exposure based on a consumption rate of one 8-ounce meal per week (0.032 kg/day), a body weight of 70 kg and reported cancer potency factors and reference doses. We identified nine species of concern (blue catfish, carp, channel catfish, cobia, crayfish, flathead catfish, red drum, spotted gar and striped bass) based on total cancer risk greater than 10(-4) or margin of exposure greater than 1, and whether or not samples collected in subsequent years resulted in lower risks. The compounds primarily responsible for the elevated risks were aldrin, dieldrin, alpha-benzene hexachloride, gamma-benzene hexachloride, heptachlor epoxide, arsenic and mercury.     

Nitrogen flux and sources in the Mississippi River Basin

Nitrogen from the Mississippi River Basin is believed to be at least partly responsible for the large zone of oxygen-depleted water that develops in the Gulf of Mexico each summer. Historical data show that concentrations of nitrate in the Mississippi River and some of its tributaries have increased by factors of 2 to more than 5 since the early 1900s. We have used the historical streamflow and concentration data in regression models to estimate the annual flux of nitrogen (N) to the Gulf of Mexico and to determine where the nitrogen originates within the Mississippi Basin. Results show that for 1980-1996 the mean annual total N flux to the Gulf of Mexico was 1,568,000 t/year. The flux was approximately 61% nitrate as N, 37% organic N, and 2% ammonium as N. The flux of nitrate to the Gulf has approximately tripled in the last 30 years with most of the increase occurring between 1970 and 1983. The mean annual N flux has changed little since the early 1980s, but large year-to-year variations in N flux occur because of variations in precipitation. During wet years the N flux can increase by 50% or more due to flushing of nitrate that has accumulated in the soils and unsaturated zones in the basin. The principal source areas of N are basins in southern Minnesota, Iowa, Illinois, Indiana, and Ohio that drain agricultural land. Basins in this region yield 800 to more than 3100 kg total N/km2 per year to streams, several times the N yield of basins outside this region. Assuming conservative transport of N in the Mississippi River, streams draining Iowa and Illinois contribute on average approximately 35% of the total N discharged by the Mississippi River to the Gulf of Mexico. In years with high precipitation they can contribute a larger percentage.     

Atmospheric nitrogen in the Mississippi River Basin--emissions, deposition and transport

Atmospheric deposition of nitrogen has been cited as a major factor in the nitrogen saturation of forests in the north-eastern United States and as a contributor to the eutrophication of coastal waters, including the Gulf of Mexico near the mouth of the Mississippi River. Sources of nitrogen emissions and the resulting spatial patterns of nitrogen deposition within the Mississippi River Basin, however, have not been fully documented. An assessment of atmospheric nitrogen in the Mississippi River Basin was therefore conducted in 1998-1999 to: (1) evaluate the forms in which nitrogen is deposited from the atmosphere; (2) quantify the spatial distribution of atmospheric nitrogen deposition throughout the basin; and (3) relate locations of emission sources to spatial deposition patterns to evaluate atmospheric transport. Deposition data collected through the NADP/NTN (National Atmospheric Deposition Program/National Trends Network) and CASTNet (Clean Air Status and Trends Network) were used for this analysis. NOx Tier 1 emission data by county was obtained for 1992 from the US Environmental Protection Agency (Emissions Trends Viewer CD, 1985-1995, version 1.0, September 1996) and NH3 emissions data was derived from the 1992 Census of Agriculture (US Department of Commerce. Census of Agriculture, US Summary and County Level Data, US Department of Commerce, Bureau of the Census. Geographic Area series, 1995:1b) or the National Agricultural Statistics Service (US Department of Agriculture. National Agricultural Statistics Service Historical Data. Accessed 7/98 at URL, 1998. http://www.usda.gov/nass/pubs/hisdata++ +.htm). The highest rates of wet deposition of NO3- were in the north-eastern part of the basin, downwind of electric utility plants and urban areas, whereas the highest rates of wet deposition of NH4+ were in Iowa, near the center of intensive agricultural activities in the Midwest. The lowest rates of atmospheric nitrogen deposition were on the western (windward) side of the basin, which suggests that most of the nitrogen deposited within the basin is derived from internal sources. Atmospheric transport eastward across the basin boundary is greater for NO3- than NH4+, but a significant amount of NH4+ is likely to be transported out of the basin through the formation of (NH4)2SO4 and NH4NO3 particles--a process that greatly increases the atmospheric residence time of NH4+. This process is also a likely factor in the atmospheric transport of nitrogen from the Midwest to upland forest regions in the North-East, such as the western Adirondack region of New York, where NH4+ constitutes 38% of the total wet deposition of N.     

Occurrence of selected surfactants in untreated and treated sewage

Several surfactants were monitored in treated and untreated sewage in nine municipal wastewater treatment plants (WWTPs) in western Austria. The nine sampled WWTPs cover a wide variety referring to size and applied treatment technology. The investigation focused on linear alkylbenzene sulphonate (LAS), quaternary ammonia compounds (QAC), nonylphenol (NP), octylphenol (OP), nonylphenolmono- (NP(1)EO) and -diethoxylates (NP(2)EO). Whereas LAS, NP, OP and NP(1,2)EO were analysed separately in the liquid phase and in the solid phase, the QACs were measured in the total sample. Total influent concentrations of LAS varied between 2.4 mg l(-1) up to 6.7 mg l(-1) whereas total effluent concentrations were in the lower microg l(-1) range (11-50 microg l(-1)). Whichever the type of treatment, a clear removal during treatment was observed. Solid liquid distribution coefficients K(d) were calculated for untreated sewage. The calculated K(d) values varied between 1300 and 3900 l kg(-1). OP was of minor importance with total influent concentrations below 1microg l(-1). NP and NP(1,2)EO were present in all analysed influents in concentrations between 1 and 35microg l(-1). Effluent concentrations were notably lower than the measured influent concentrations. K(d) values for NP varied between 500 and 6600 l kg(-1), for NP(1)EO between 800 and 2700 l kg(-1) and for NP(2)EO between 100 and 1800 l kg(-1). From the QACs several alkyl benzyl (BAC), dialkyl (DDAC) and trialkyl (ATAC) ammonium chlorides with varying alkyl chain lengths were analysed. Highest total concentrations in the influents to the WWTPs were observed for the BAC-C12 and the ATAC-C16 homologues. Effluent concentrations were notably lower compared to influent concentrations, indicating removal by adsorption and/or biodegradation. The influence of the removal by adsorption increased with increasing alkyl chain length.     

Pesticides in the atmosphere of the Mississippi River Valley, part I--rain

Lysosomal responses are widely accepted cellular effect biomarkers of general stress. Up to now, these biomarkers have been analysed by means of conventional techniques based on enzyme histochemical methods, where lysosomal enzymes such as acid phosphatase and beta-glucuronidase (beta-GUS) have been employed as markers of lysosomes. The aim of the present work was to develop more advanced and sensitive methods based on the use of polyclonal antibodies to measure lysosomal enzymes in different sentinel organisms. For this purpose, we have studied the cross-reactivity of two commercial polyclonal antibodies against the lysosomal enzymes acid phosphatase and beta-GUS with molluscan digestive gland by means of immunoblotting and immunohistochemistry. The antibody against acid phosphatase cross-reacted specifically with the lysosomal fraction of the digestive gland, while unspecific immunoreaction occurred with digestive gland whole homogenates and tissue sections. The antibody against beta-GUS cross-reacted specifically with digestive gland whole homogenates and tissue sections. The cross-reactivity of this antibody was tested also in crab hepatopancreas and mullet liver where the same successful results were obtained. The second aim of the present study was to test if the immuno-based approach was sensitive enough to detect lysosomal alterations provoked by contaminants. For this purpose two experiments were carried out with mussels treated with cadmium in two ways: in vivo treatment by injection and in vitro treatment using digestive gland explants. Afterwards immunoblotting studies with the antibody against beta-GUS were applied and immunoreactive bands were quantified by means of a gel analysis programme. We found that beta-GUS protein levels were higher in treated mussels when compared with controls in either in vivo or in vitro treatments. All these data suggest that the polyclonal antibody against beta-GUS is adequate to be used in immuno-based approaches to detect contaminant-induced lysosomal alterations.     

Pesticides in the atmosphere of the Mississippi River Valley, part II--air

Weekly composite air samples were collected from early April through to mid-September 1995 at three paired urban and agricultural sites along the Mississippi River region of the Midwestern United States. The paired sampling sites were located in Mississippi, Iowa, and Minnesota. A background site, removed from dense urban and agricultural areas, was located on the shore of Lake Superior in Michigan. Each sample was analyzed for 49 compounds; of these, 21 of 26 herbicides, 13 of 19 insecticides, and 4 of 4 related transformation products were detected during the study, with most pesticides detected in more than one sample. The maximum number of pesticides detected in an air sample was 18. Herbicides were the predominant type of pesticide detected at every site. Detection frequencies of most herbicides were similar at the urban and agricultural sites in Iowa and Minnesota. In Mississippi, herbicides generally were detected more frequently at the agricultural site. The insecticides chlorpyrifos, diazinon, and carbaryl, which are used in agricultural and non-agricultural settings, were detected more frequently in urban sites than agricultural sites in Mississippi and Iowa. Methyl parathion was detected in 70% of the samples from the Mississippi agricultural site and at the highest concentration (62 ng/m3 air) of any insecticide measured in the study. At the background site, dacthal (100%), atrazine (35%), cyanazine (22%), and the (primarily atrazine) triazine transformation products CIAT (35%) and CEAT (17%) were detected most frequently, suggesting their potential for long-range atmospheric transport.     

Occurrence of cotton herbicides and insecticides in playa lakes of the High Plains of West Texas

During the summer of 1997, water samples were collected and analyzed for pesticides from 32 playa lakes of the High Plains that receive drainage from both cotton and corn agriculture in West Texas. The major cotton herbicides detected in the water samples were diuron, fluometuron, metolachlor, norflurazon, and prometryn. Atrazine and propazine, corn and sorghum herbicides, were also routinely detected in samples from the playa lakes. Furthermore, the metabolites of all the herbicides studied were found in the playa lake samples. In some cases, the concentration of metabolites was equal to or exceeded the concentration of the parent compound. The types of metabolites detected suggested that the parent compounds had been transported to and had undergone degradation in the playa lakes. The types of metabolites and the ratio of metabolites to parent compounds may be useful in indicating the time that the herbicides were transported to the playa lakes. The median concentration of total herbicides was 7.2 microg/l, with the largest total concentrations exceeding 30 microg/l. Organophosphate insecticides were detected in only one water sample. Further work will improve the understanding of the fate of these compounds in the playa lake area.     

Herbicide concentrations in the Mississippi River Basin-the importance of chloroacetanilide herbicide degradates

The proportion of chloroacetanilide herbicide degradates, specifically the ethane sulfonic (ESA) and oxanilic (OA) acids, averaged 70% of the total herbicide concentration in samples from the Upper Mississippi River. In samples from the Missouri River and the Ohio River, the proportion of chloroacetanilide degradates in the total herbicide concentration was much less, 24% and 41%, respectively. The amount of tile drainage throughout the Mississippi River Basin appeared to be related to the occurrence and distribution of chloroacetanilide degradates in water samples. Pesticide concentrations in streams of the Mississippi River Basin have been well characterized. However, recent research demonstrates that in order to more fully understand the fate and transport of pesticides, the major pesticide degradates need to be included in the analysis. From March 1999 through May 2001, water samples from four major junctures of the Mississippi River Basin were collected and analyzed for a suite of herbicides and their degradate compounds. Each sampling site was selected to represent a major part of the Mississippi River: upper and lower Mississippi, Missouri and Ohio Rivers. Each basin has unique landscape variables, geology, hydrology, precipitation, and land use, which is reflected in the pesticide content at the most downstream sample site near the mouth of the Mississippi River. Atrazine was the most frequently detected herbicide (detected in 97% of the samples), followed by metolachlor (60%), and acetochlor (31%). The most frequently detected degradates were metolachlor ESA (69%), followed by deethylatrazine (62%), metolachlor OA (37%), and alachlor ESA (37%). Metolachlor ESA was detected more frequently than its parent compound (69 vs. 60%), as was alachlor ESA (37 vs. 9%). After an improvement was made in the analytical method, metolachlor ESA was detected in every sample, metolachlor OA in 89% of the samples, alachlor ESA in 84%, acetochlor ESA in 71%, and acetochlor OA in 66%.     

Occurrence of pesticides in rain and air in urban and agricultural areas of Mississippi, April-September 1995

In April 1995, the US Geological Survey began a study to determine the occurrence and temporal distribution of 49 pesticides and pesticide metabolites in air and rain samples from an urban and an agricultural sampling site in Mississippi. The study was a joint effort between the National Water-Quality Assessment and the Toxic Substances Programs and was part of a larger study examining the occurrence and temporal distribution of pesticides in air and rain in the Mississippi River basin. Concurrent high-volume air and wet-only deposition samples were collected weekly. The air samplers consisted of a glass-fiber filter to collect particles and tandem polyurethane foam plugs to collect gas-phase pesticides. Every rain and air sample collected from the urban and agricultural sites had detectable levels of multiple pesticides. The magnitude of the total concentration was 5-10 times higher at the agricultural site as compared to the urban site. The pesticide with the highest concentration in rain at both sites was methyl parathion. The pesticide with the highest concentration in the air samples from the agricultural site was also methyl parathion, but from the urban site the highest concentration was diazinon followed closely by chlorpyrifos. More than two decades since p,p'-DDT was banned from use in the United States, p,p'-DDE, a metabolite of p,p'-DDT, was detected in every air sample collected from the agricultural site and in more than half of the air samples from the urban site.     

Analysis of selected herbicide metabolites in surface and ground water of the United States

One of the primary goals of the US Geological Survey (USGS) Laboratory in Lawrence, Kansas, is to develop analytical methods for the analysis of herbicide metabolites in surface and ground water that are vital to the study of herbicide fate and degradation pathways in the environment. Methods to measure metabolite concentrations from three major classes of herbicides--triazine, chloroacetanilide and phenyl-urea--have been developed. Methods for triazine metabolite detection cover nine compounds: six compounds are detected by gas chromatography/mass spectrometry; one is detected by high-performance liquid chromatography with diode-array detection; and eight are detected by liquid chromatography/mass spectrometry. Two metabolites of the chloroacetanilide herbicides--ethane sulfonic acid and oxanilic acid--are detected by high-performance liquid chromatography with diode-array detection and liquid chromatography/mass spectrometry. Alachlor ethane sulfonic acid also has been detected by solid-phase extraction and enzyme-linked immunosorbent assay. Six phenylurea metabolites are all detected by liquid chromatography/mass spectrometry; four of the six metabolites also are detected by gas chromatography/mass spectrometry. Additionally, surveys of herbicides and their metabolites in surface water, ground water, lakes, reservoirs, and rainfall have been conducted through the USGS laboratory in Lawrence. These surveys have been useful in determining herbicide and metabolite occurrence and temporal distribution and have shown that metabolites may be useful in evaluation of non-point-source contamination.     

Occurrence and risk assessment of acidic pharmaceuticals in the Yellow River, Hai River and Liao River of north China

Pharmaceuticals in the aquatic environment have received great attentions from the general and scientific community due to their potential impacts on ecological and human health. We investigated the occurrence of twelve acidic pharmaceuticals and herbicides (salicylic acid, clofibric acid, ibuprofen, gemfibrozil, fenoprofen, naproxen, ketoprofen, mefenamic acid, tolfenamic acid, diclofenac, meclofenamic acid and indomethacin) in surface waters of the Yellow River, Hai River and Liao River in north China during the wet and dry seasons and assessed the potential risks to aquatic organisms posed by these acidic compounds. Seven acidic compounds were detected in the rivers, including five non-steroidal anti-inflammatory drugs (salicylic acid, ibuprofen, diclofenac, mefenamic acid and naproxen), and two blood lipid regulators (clofibric acid and gemfibrozil). The concentrations for acidic pharmaceuticals in the Yellow River and Liao River were in most cases higher in the dry season than in the wet season, but the concentrations of acidic compounds in the Hai River were generally higher in July than in November. High concentrations of these detected compounds in the Yellow River, Hai River and Liao River were found more frequently at those sites located in metropolitan areas, lower reaches or river confluences. Only diclofenac and ibuprofen were found to have medium to high risks in the three rivers based on the calculated risk quotients.     

Occurrence and fate of linear and branched alkylbenzenesulfonates and their metabolites in surface waters in the Philippines

Laguna de Bay in the Philippines is one of the largest freshwater lakes in Asia and is considered a primary source of drinking water, but also receives daily discharges of effluent from both domestic and industrial activities. Branched alkylbenzenesulfonates (ABS), which were banned in Europe and withdrawn from the market in the U.S. since the mid-1960s, but not in Southeast Asia, and linear alkylbenzenesulfonates (LAS) are anionic surfactants used in detergent formulations and are therefore main components of effluent discharges. The presence of both LAS and ABS in several water streams in the catchment area of Laguna de Bay was determined using liquid chromatography-mass spectrometry (LC-MS). The concentration levels of LAS (1.2-73 and 2.2-102 microg l(-1)) and ABS (1.1-75 and 1-66 microg l(-1)) in some tributaries of Laguna de Bay and its outlet (Pasig River) to Manila Bay were assessed in December 1999 and March 2000, respectively. The LAS/ABS ratio was calculated as an indication of the extent of the distribution and fate of these surfactants in the surface water. The nearer the location to the metropolitan area of Manila, the higher the levels of LAS and ABS detected in the waters. Moreover, the extent of biodegradation was investigated by monitoring their alkyl homologue distribution and the presence of sulfophenylcarboxylate (SPC) metabolites. Similarly, differences in the levels of SPC and the homologues were apparent at the different sampling points. Presumably, even the quite recalcitrant ABS form SPCs under the conditions present in Southeast Asia. Since wastewater treatment facilities are not well established in developing countries like the Philippines, the call for the use of environmentally friendly chemicals is of even higher significance.     

Occurrence and fate of antibiotics in the Seine River in various hydrological conditions

Occurrence and fate of 17 antibiotics were investigated in the aqueous phase of river water under different hydrological conditions at 5 sampling locations in the Seine River inner estuary. The target analytes belonged to 4 groups: quinolones, sulfonamides, nitro-imidazoles and diaminopyrimidines. This six-month survey (from January to June 2006) showed that different compounds were occurring at individual concentrations reaching 544 ng L(-)(1) (sulfamethoxazole). All 17 compounds were detected at least once in the survey. Sulfamethoxazole was detected in every sample, and showed the highest concentrations. Norfloxacin and flumequine were found to be the most ubiquitous quinolones, with detection frequencies of 33 and 75% respectively at the most contaminated site (Poses). Investigations concerning the origins of this contamination were made by means of a longitudinal profile along the Seine River between Paris and Poses. It showed large inputs of norfloxacin, ofloxacin, trimethoprim and sulfamethoxazole from wastewater treatment plants, with an increase in norfloxacin and sulfamethoxazole concentrations of 84% and 70% respectively, both reaching 155 ng L(-)(1) in the river, downstream from a wastewater outlet. The detected compounds showed different dissipation patterns and behaviours under different hydrological conditions. Higher inputs of norfloxacin were found in low flow conditions, which were rapidly attenuated along the stream. In contrast, sulfamethoxazole inputs were increasing in high flow conditions, and dissipation of this compound was found to be slow. Similar behaviour was observed for the synergist trimethoprim. Flumequine was also frequently detected and its input increased during flood events.     

Methylmercury input to the Mississippi River from a large metropolitan wastewater treatment plant

Methylmercury (MeHg) and total mercury (THg) inputs to the Mississippi River from a large metropolitan wastewater treatment plant were measured to characterize the relative contribution of the treatment plant to in-stream loads of these contaminants. Concentrations of MeHg and THg were determined in filtered and unfiltered whole water samples collected weekly from the treatment plant effluent stream and from the river upstream of the plant discharge. Unfiltered MeHg concentrations in the plant effluent ranged from 0.034 to 0.062 ng L(-1) and were always less than those in the river (range: 0.083-0.227 ng L(-1)). The MeHg loading to the river from the treatment plant ranged from 0.026 to 0.051 g d(-1) and averaged 0.037 g d(-1) over the 13-week sampling period. The in-stream MeHg load in the river upstream varied widely depending on hydrologic conditions, ranging from 0.91 to 18.8 g d(-1) and averaging 4.79 g d(-1). The treatment plant discharge represented 1.6%, on average, of the in-stream MeHg load, ranging from 0.2 to 3.5% depending on flow conditions in the river. MeHg in treatment plant effluent was primarily in the filtered phase (mean: 57%, <0.2 microm), but in the river the filtered/unfiltered ratio (F/UF) was typically less than 30% except during a major precipitation runoff event, when F/UF increased to 78%. The MeHg/THg ratio in unfiltered treatment plant effluent varied little (range: 1.6-1.9%), suggesting that THg concentration can serve as a relatively accurate proxy for MeHg concentration in this effluent stream. Supplemental sampling of the treatment plant influent stream showed that removals of MeHg and THg across the treatment process averaged 97% and 99%, respectively. These results show the treatment plant to be effective in removing MeHg and THg from wastewater and in minimizing its impact on Hg levels in the receiving water.     

The occurrence of selected pharmaceuticals in wastewater effluent and surface waters of the lower Tyne catchment

This paper presents the results of a survey of the wastewater effluent and surface waters of the lower river Tyne, UK. Samples were analysed by reversed-phase high-performance liquid chromatography-electrospray tandem mass spectrometry following solid phase extraction, for the presence of 13 pharmaceuticals selected from the priority lists of the UK Environment Agency and the Oslo and Paris Commission (OSPAR). The pharmaceutical compounds measured were acetyl-sulfamethoxazole, clofibric acid, clotrimazole, dextropropoxyphene, diclofenac, erythromycin, ibuprofen, mefenamic acid, paracetamol, propranolol, sulfamethoxazole, tamoxifen and trimethoprim. Of the wastewater treatment works (WTW) samples (n=9) analysed, all compounds except sulfamethoxazole and acetyl-sulfamethoxazole were detected at concentrations ranging from 11 to 69,570 ng l(-1) (in raw effluent). In the surface water samples (n=18), clotrimazole, dextropropoxyphene, erythromycin, ibuprofen, propranolol, tamoxifen and trimethoprim were detected at concentrations ranging from 4 to 2370 ng l(-1). Results of this study show that various pharmaceutical compounds are effectively reduced during their passage through a tertiary wastewater treatment works, whilst others are sufficiently persistent to occur in estuarine systems.     

Occurrence of selected pharmaceuticals in an agricultural landscape, western Lake Erie basin

The occurrence of 18 commonly used pharmaceuticals was investigated in an agricultural area, which is primarily affected by runoff from agricultural fields and septic systems, on the coastline of Maumee Bay, within the western Lake Erie basin. Selected pharmaceuticals were detected in surface water, except clofibric acid and fluoxethine. The most frequently detected compounds were caffeine (88%), carbamazepine (57%) and paraxanthine (56%). Caffeine, carbamazepine, ibuprofen and paraxanthine were detected with maximum concentrations of 4.2, 1.2, 2.8 and 1.8 μg L⁻¹, respectively. However, no compound was detected in any sediment samples. In a field receiving biosolids application, pharmaceuticals were detected in the field tile drainage following biosolids application but not in soil. The occurrence of pharmaceuticals in surface water can be linked to the use of septic systems.     

国道314线库尔勒孔雀河大桥检测与荷载试验

详细介绍了新疆库尔勒孔雀河大桥的检测与荷载试验情况,通过对大桥桥道T梁及拱肋的应变、挠度、自振特性及振动响应测试、对大桥的承载能力进行了分析评价,以为大桥的加固提供依据。     

Occurrence and biological effect of exogenous steroids in the Elkhorn River, Nebraska, USA

Recent studies of surface waters in North America, Japan and Europe have reported the presence of steroidogenic agents as contaminants. The current study has three objectives: 1) to determine if steroidogenic compounds are present in the Elkhorn River, 2) to determine if sediments collected from the Elkhorn River can act as a source of steroidogenic compounds to aquatic organisms, and 3) to determine if site-specific biological effects are apparent in the hepatic gene expression of fathead minnows. Evidence was obtained using three approaches: 1) deployment of polar organic chemical integrative samplers (POCIS), 2) deployment of caged fathead minnows, and 3) a laboratory experiment in which POCIS and fish were exposed to sediments from the deployment sites. Deployment sites included: the Elkhorn River immediately downstream from a Nebraska wastewater treatment plant, two waterways (Fisher Creek and Sand Creek) likely to be impacted by runoff from cattle feeding operations, and a reference site unlikely to be impacted by waste water inputs. The POCIS extracts were analyzed for a number of natural steroids and metabolites, as well as four different synthetic steroids: ethinylestradiol, zearalonol, 17beta-trenbolone and melengestrol acetate. Estrogenic and androgenic metabolites, as well as progesterone and trace levels of melengestrol acetate were detected in POCIS deployed at each site. POCIS deployed in tanks containing field sediments from the four sites did not accumulate the synthetic steroids except for ethinylestradiol, which was detected in the aquarium containing sediments collected near the wastewater treatment plant. Fish deployed in Sand Creek and at the wastewater treatment plant experienced significantly elevated levels of gene expression for two genes (StAR and P450scc) relative to those deployed in Fisher Creek. Fish exposed to the sediments collected from Sand Creek had significantly higher levels of hepatic StAR and P450scc gene expression than did fish exposed to sediments from the two other field sites, as well as the no-sediment control tank. In conclusion: 1) detectable levels of steroidogenic compounds were detected in passive samplers deployed in the Elkhorn River, 2) sediments do not appear to be a significant source for steroidogenic compounds, and 3) site-specific differences were found in mRNA expression among the different treatment groups of fish; however, a functional explanation for these differences is not readily forthcoming.     

冷弯型钢房屋墙体立柱临界屈曲荷载能量解

冷弯薄壁型钢低层住宅房屋体系的墙体一般由墙体密立柱、墙面围护材料组成 墙面材料不仅是建筑的需要 ,同时也能在一定程度上对墙体立柱提供有效的支承作用 通过简化推导 ,建立起了考虑墙板的支承效应时墙体立柱的力学模型 ,并在弹性范围内 ,分别利用Rayleigh Ritz法推导出了墙体立柱两端简支、两端固定、一端固定一端自由和一端简支一端固定等 4种典型边界条件下墙体立柱的整体屈曲临界荷载 ,并将其转化成为常规形式的表达式 ,可供设计、研究参考