Transport of veterinary antibiotics in overland flow following the application of slurry to arable land

The environment may be exposed to veterinary medicines administered to livestock due to the application of organic fertilisers to land. Slurry is often spread on to fields following the harvest of the previous crop. Despite recommendations to do so, the slurry may not be ploughed into the soil for some time. If precipitation occurs before incorporation then it is likely that the slurry and any antibiotic residues in the slurry will be transported towards surface waters in overland flow. This phenomenon has been investigated in a plot study and transport via 'tramlines' has been compared to that through crop stubble. Three veterinary antibiotics, from the tetracycline, sulphonamide and macrolide groups, were applied to the plots in pig slurry. Twenty four hours after the application the plots were irrigated. Following this the plots received natural rainfall. Sulphachloropyridazine was detected in runoff from the tramline plot at a peak concentration of 703.2 microgl(-1) and oxytetracycline at 71.7 microgl(-1). Peak concentrations from the plot that did not contain a tramline were lower at 415.5 and 32 microgl(-1), respectively. In contrast, tylosin was not detected at all. Mass losses of the compounds were also greater from the tramline plot due to greater runoff generation. These did not exceed 0.42% for sulphachloropyridazine and 0.07% for oxytetracycline however.     

Evaluation of municipal sewage treatment systems for pollutant removal efficiency by measuring levels of micropollutants

In order to evaluate the municipal sewage treatment systems used at Harbin municipal sewage treatment plant for their pollutant removal efficiency, raw sewage and effluent samples at different treatment stages from the sewage treatment systems were taken, priority pollutants (PPs) were identified and quantified using gas chromatography-mass spectrometry (GC-MS) and inductively coupled plasma-atomic emission spectrograph (ICP-AES). The test results indicated that there were one hundred and fifty species of organic pollutants identified in the raw sewage sample, and only ten species of PPs in all the sewage samples. The levels of dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), di-n-octyl phthalate (DnOP) in the sewage samples were 0.779-0.111 microg l(-1), 1.977-0.022 microg l(-1), 6.411-2.194 microg l(-1) and 7.152-2.953microg l(-1), respectively, and most of these phthalate esters (PAEs) were removed through anaerobic/aerobic (A/O) process; The levels of alachlor, acetochlor, atrazine were 0.074-0.021 microg l(-1), 0.160-0.096 microg l(-1) and 0.238-0.184 microg l(-1), respectively, and the total removal efficiency of atrazine was poorest through the sewage treatment systems. The levels of Cu, Cr, Se, Hg, Ni and Zn were 0.0030-0.2327 mg l(-1). It is therefore concluded from these results that the sewage treatment systems were efficient in removing most of the organic and inorganic compounds in this study, and so, the discharged effluent could cause little of the secondary pollution of the aquatic environment.     

A practical demonstration in modelling diclofenac and propranolol river water concentrations using a GIS hydrology model in a rural UK catchment

An existing GIS hydrology water quality model, LF2000-WQX, was applied to predict the concentrations of the pharmaceuticals diclofenac and propranalol in catchments. As a practical exercise the predominantly rural Tamar (UK) catchment was chosen. Consumption, excretion, and fate data were used to estimate the pharmaceutical input load for the model. The predicted concentrations throughout most of the catchment were 1 ng/L or less under low flow (90th percentile) conditions. However, at a few locations, downstream of small sewage treatment plants, concentrations above 25 ng/L were predicted. This exercise shows that it is relatively straightforward to predict the concentrations of new and emerging organic microcontaminants in real catchments using existing GIS hydrology water quality models. Further testing will be required to establish their accuracy.     

Fate of 5-fluorouracil, doxorubicin, epirubicin, and daunorubicin in hospital wastewater and their elimination by activated sludge and treatment in a membrane-bio-reactor system

Antineoplastic agents are applied in cancer therapy and end up in hospital wastewater by human excretions. In this study, the raw wastewater of the sewer of the oncologic in-patient treatment ward of the Vienna University Hospital was monitored for 98 d over 2 years for the cytostatics 5-fluorouracil (5-FU), doxorubicin (DOX), epirubicin, and daunorubicin. In a next step, the elimination of the drugs by a membrane-bio-reactor system was investigated. In addition, their fate in wastewater and elimination by activated sludge was investigated with radio-labelled substances. During the monitoring periods, concentration levels ranging from <8.6 to 124 microgl(-1) for 5-FU and from <0.26 to 1.35 microgl(-1) for DOX were determined. The concentrations analysed fitted the lower ranges calculated by an input-output model. Treatment of oncologic wastewater in the membrane bio-reactor as well as the analysis of the effluents of the Vienna University Hospital resulted in concentrations below the limit of detection. Investigations with radio-labelled compounds showed that 5-FU is eliminated from the liquid phase below the limit of detection. But, up to 25% of radio-labelled equivalents of the drug's amount were found in the gaseous phase and only a marginal part in the solid phase, this indicates that at least one part of the drug is biodegraded. For the anthracyclines more than 90% was eliminated from the liquid phase. In this case, adsorption to suspended solids seems to be the major elimination pathway, as up to 30% of the radio-labelled equivalents of the drug's amount was detected in the solid phase. Our results indicate that the investigated anticancer drugs are eliminated by sewage treatment plants, either by biodegradation or adsorption.     

Spatial and temporal analysis of pharmaceutical concentrations in the upper Tennessee River basin

The behavior of pharmaceutical compounds in aquatic ecosystems is not well defined. In order to determine spatial and temporal variations in concentrations of pharmaceuticals in the Tennessee River, water samples were collected from multiple points along the river and at the inflow of major tributaries. Sampling structure was designed to investigate trends between surface and subsurface samples, seasonal trends (winter, spring, summer, and fall), the direct influence of sewage treatment plants (upstream versus downstream), and the effect of downstream distance on pharmaceutical concentrations. All samples were quantified via solid phase extraction followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). This method yielded reproducible quantitation at low parts per trillion (ng L(-1)) levels for all 14 analytes (acetaminophen, atorvastatin, caffeine, carbamazepine, ciprofloxacin, diltiazem, fluoxetine, levofloxacin, lovastatin, norfluoxetine, ranitidine, sertraline, sulfamethoxazole, and trimethoprim). Correlation analyses (depth, distance) and repeated-measures ANOVAs (season, sewage treatment plant proximity) were used to determine statistically significant trends for frequently detected pharmaceuticals (caffeine, carbamazepine, sulfamethoxazole). Caffeine and sulfamethoxazole were found to vary by season in subsurface samples; spring exhibited the highest concentrations. Carbamazepine varied in proximity to sewage treatment plant outfall with subsurface samples yielding greater concentrations downstream than upstream. In addition, individual pharmaceuticals displayed positive correlation between surface and subsurface samples and negative correlation with downstream distance from the headwaters.     

Analysis of the health risk of exposure to breast milk mercury in infants in Taiwan

The aim of this study was to assess the total concentration and health risk to infants of breast milk mercury in urban mothers and mothers married to fishermen in relation to fish intake in Taiwan. A total of sixty-eight healthy mothers were recruited for the study. The breast milk mercury geometric mean concentration was 2.02 microgl(-1) (n=56, range: 0.24-9.45 microgl(-1)) for the city group and 2.04 microgl(-1) (n=12, range: 0.26-8.62 microgl(-1)) for the fishermen's group. Of the three sources of mercury exposure (i.e., ingestion (breast milk), inhalation (ambient air), and dermal exposure (shower)), breast-feeding was found to be the largest (96.3-99.6% of the total). From a Monte Carlo simulation, in which methyl mercury accounted for about 50% of total mercury, the hazard quotient (exposure estimate/oral minimal risk level or target organ toxicity dose) exceeded 1.0 for 12.9% of urban babies and 18.8% of fishermen's babies (chronic oral minimal risk level and target organ toxicity dose: 3 x 10(-4)mgkg(-1)d(-1)). The calculated mercury exposure was 3.02 x 10(-1) microgkg(-1)d(-1) for a 3.49 kg urban baby boy and 3.06 x 10(-1) microgkg(-1)d(-1) for a 3.44 kg urban baby girl. These results suggest the life style of mothers (eating raw fish and shellfish such as used in "Sashimi" and "Sushi," and vitamin supplementation) may influence the mercury concentration in breast milk.     

Occurrence of psychoactive compounds and their metabolites in groundwater downgradient of a decommissioned sewage farm in Berlin (Germany)

Purpose

Psychoactive compounds??meprobamate, pyrithyldione, primidone, and its metabolites, phenobarbital, and phenylethylmalonamide??were detected in groundwater within the catchment area of a drinking water treatment plant located downgradient of a former sewage farm in Berlin, Germany. The aim of this study was to investigate the distribution of the psychoactive compounds in anoxic groundwater and to assess the risk of drinking water contamination. Groundwater age was determined to achieve a better understanding of present hydrogeological conditions.

Methods

A large number of observation and production wells were sampled. Samples were analyzed using solid-phase extraction and ultrahigh-performance liquid chromatography?Ctandem mass spectrometry. Groundwater age was estimated using the helium?Ctritium (³He?C³H) dating method.

Results

Concentrations of psychoactive compounds up to 1???g/L were encountered in the contamination plume. Generally, concentrations of phenobarbital and meprobamate were the highest. Elevated concentrations of the analytes were also detected in raw water from abstraction wells located approximately 2.5?km downgradient of the former sewage farm. Concentrations in the final drinking water were below the limit of quantification owing to dilution. The age of shallow groundwater samples ranged from years to a decade, whereas groundwater was up to four decades old at 40?m below ground. Concentrations of the compounds increased with groundwater age.

Conclusions

Elevated concentrations of psychoactive drugs indicate a strong persistence of these compounds in the environment under anoxic aquifer conditions. Results suggest that the heritage of sewage irrigation will affect raw water quality in the area for decades. Therefore, further monitoring of raw and final drinking water is recommended to ensure that contaminant concentrations remain below the health-based precautionary value.     

A case study of molinate application in a Portuguese rice field: herbicide dissipation and proposal of a clean-up methodology

This study was designed to monitor molinate losses in surface and underground waters during Ordram application in a rice field situated in central Portugal. Water samples were collected from different sites, before, during and about one month and a half after Ordram application. Molinate quantification was based on a solid-phase microextraction (SPME) method followed by gas chromatography with flame photometric detector (GC-FPD) analysis, and led to the conclusion that the herbicide was dissipated in the environment, reaching levels as high as 3.9 microgl(-1) in underground water and 15.8 microgl(-1) in the river receiving tail waters. The feasibility of the application of treatment methodologies based on adsorption or biodegradation as processes to remove molinate from real-world waters was assessed. These methods seem suitable to reduce molinate concentrations to values in the range of the legally recommended limits (<0.5 microgl(-1)).     

Dioxin-like compounds in Australian sewage sludge--review and national survey

An Australian survey of dioxin-like compounds in sewage sludge was conducted in two parts (a) a national survey, and (b) a time-study. All sewage sludge samples analysed as part of these studies had low overall concentrations of dioxin-like compounds. Out of 37 samples, all except one, were within the reported concentration range of soil within the Australian environment. The mean concentration of dioxin-like compounds in the Australian sewage sludge survey of 2006 was found to be 5.6 (s.d. 4.5) ng WHO(05) TEQkg(-1) (n=14) and were within the range of 1.2-15.3 ng WHO(05) TEQ kg(-1). All the Australian sewage sludge samples cited in these studies were below the Victorian EPA "investigation limit" of 50 ng WHO(98) TEQ kg(-1), and well below the European proposed guidelines of 100 ng I-TEQ kg(-1). The burden of dioxin-like compounds in Australian sewage sludge is low and its land application as biosolids is not likely to pose a problem. A general positive relationship was found between population of the town producing the waste and both dioxin-like PCDD/Fs and dioxin-like PCBs. The one exception to this trend was sludge from a town that had a history of smelting and had a relatively high burden of dioxin-like compounds. Sludge from one rural WWTP also had a higher burden of dioxin-like compounds. The treatment plant services a geographically isolated town with a low population and no known emitters of dioxin-like compounds. However, this sample also had a relatively high burden of dioxin-like PCBs, which could be the source of the dioxin-like PCDD/Fs found in this sludge. The time study analyzing sludges from three WWTP from the same city between the years 2002 and 2006 found no apparent difference between WWTPs, but a statistically significant decline of 1.49 ng WHO(05) TEQ kg(-1) per year. Also, a comprehensive review of the scientific literature, presents typical levels and sources of dioxin-like compounds in international sewage sludges.     

Determination of fluoroquinolone antibiotics in wastewater effluents by liquid chromatography-mass spectrometry and fluorescence detection

The occurrence of quinolone antibiotics (QAs) was investigated in wastewater effluents and surface river/lake waters in the US and Canada by using solid-phase extraction with mixed phase cation exchange disk cartridge and liquid chromatography-mass spectrometry (LC-MS) and liquid chromatography fluorescence detection (LC-FLD). Ofloxacin (OFL) was detected in secondary and final effluents of a wastewater treatment plant (WWTP) in East Lansing, Michigan, at concentrations of 204 and 100 ng/l, respectively. The mass flow calculation, estimated by multiplying the OFL concentration in the final effluent by the average influent volume of the WWTP, showed that the discharge of OFL to the river was 4.8 g/day. The OFL concentrations in wastewater effluents measured in this study are comparable to or less than those observed in several European countries. QAs were not detected in river and lake waters analyzed in this study, which may due to dilution effects and to the higher detection limits, relative to those reported previously. OFL concentrations were approximately 1-2 orders of magnitude lower than the EC50 concentrations for environmental bacterium. However, greater concentrations of other QAs in sewage sludge from WWTPs may result in cumulative effects. Considering that the sewage sludge is applied to the land as fertilizers, soil-dwelling organisms could experience greater exposures to such antibiotics. Monitoring studies of QAs in sewage from WWTPs and in sediment/soil near aquaculture facilities and livestock farms will be necessary for the evaluation of the environmental distribution and risk of these compounds.     

Short- and long-chain perfluorinated acids in sewage sludge from Shanghai, China

Perfluorinated acids (PFAs) are the subject of increasingly intense environmental research. In this study, sewage sludge samples were collected from 25 wastewater treatment plants (WWTPs) in Shanghai, China to evaluate the levels and profile of C3-C14 PFAs. The results showed a ubiquitous PFAs contamination of sewage sludge in Shanghai with the total PFAs (∑PFAs) range of 126-809 ng g(-1)dw. Perfluorooctanoic acid (PFOA) was found to be the dominant PFA pollutant and its concentration ranged from 23.2 to 298 ng g(-1)dw, much higher than the levels in other countries. Moreover, concentrations of short-chain PFAs (相似文献   

Phytotoxicity to and uptake of enrofloxacin in crop plants

Phytotoxicity of enrofloxacin on crop plants Cucumis sativus, Lactuca sativa, Phaseolus vulgaris and Raphanus sativus was determined in a laboratory model: the effect of 50, 100 and 5000 microgl(-1) were evaluated after 30 days exposure by measuring post-germinative growth of primary root, hypocotyl, cotyledons and leaves. Concentrations between 50 and 5000 microgl(-1) induced both toxic effect and hormesis in plants, by significantly modifying both length of primary root, hypocotyl, cotyledons and the number/length of leaves. A toxic effect is induced by high concentration (5000 microgl(-1)), while hormesis occurs at low concentrations (50 and 100 microgl(-1)). A continuum between toxic effect and hormesis is found in the four plant species. Both toxic effect and hormesis can be related to an efficient plant drug uptake, in the order of microgg(-1). Plants are able to metabolize enrofloxacin into ciprofloxacin, as also happens in animals; Cucumis, Lactuca and Phaseolus biologically convert about one quarter of stored enrofloxacin. The ecological implication of enrofloxacin contamination in terrestrial environments is discussed.     

Effects of 3-chlorobiphenyl on photosynthetic oxygen production, glutathione content and detoxication enzymes in the aquatic macrophyte Ceratophyllum demersum

Organic contaminants of environmental concern such as polychlorinated biphenyls have dispersed widely throughout the ecosystems and accumulate in living organisms, and a variety of adverse biological effects have been reported. In this study, we investigated the effects of 3-chlorobiphenyl in the aquatic macrophyte Ceratophyllum demersum and the capacity of its detoxication system. After 24 h of exposure to various concentrations of 3-chlorobiphenyl, the total glutathione content (tGSH) was determined and the dose-response curves for glutathione reductase (GR) and microsomal/cytosolic glutathione S-transferases (m- and c-GSTs, respectively) were established. C. demersum showed a decrease of photosynthesis after exposure to 3-chlorobiphenyl, although only significantly at 5 microgl(-1). At 0.005 and 0.05 microgl(-1) the GR, m-GST and c-GST activities were significantly increased and concomitantly a non-significant effect on total GSH was observed. At 0.5 microgl(-1), GR as well as c-GST were still significantly induced, while at 5 microgl(-1) none of the enzymes were activated. These results show that detoxication through glutathione conjugation takes place at low concentrations of 3-chlorobiphenyl, while concentrations in the order of parts per billion cause the inactivation of the enzymatic systems evaluated, enough to place C. demersum in an important physiological stress condition.     

Effects of formulations of the fungicide, pentachloronitrobenzene on early life stage development of the Japanese medaka (Oryzias latipes)

Quintozene is a fungicide containing the active ingredient, pentachloronitrobenzene (PCNB) that is used to control "snow mold" on golf courses in temperate regions of North America. In this study, quintozene and a formulation of quintozene widely used on golf courses, FFII were tested for toxicity to early life stages of the Japanese medaka, Oryzias latipes. For medaka exposed in static non-renewal assays to quintozene for 17d from the fertilized egg stage to yolk resorption at the fry stage, the LC(50) for mortality was a nominal concentration of 707 microgl(-1) and the effective concentration for 50% hatch (i.e. EC(50)) was a nominal concentration of 71 microgl(-1). Eggs and fry showed developmental abnormalities, including ocular malformations and retarded development of the brain, notochord, organs and body segmentation, which were interpreted as teratogenic responses to exposure to PCNB. For medaka exposed to quintozene, the LOECs for abnormalities of the eye and all other developmental abnormalities were 750 and 100 microgl(-1), respectively. In medaka exposed to the FFII formulation, similar patterns of mortalities, reduced hatching success and developmental abnormalities were observed, but at higher test concentrations that were consistent with the proportion of quintozene in the formulation. For medaka exposed to the formulation, the LOECs for abnormalities of the eye and all other developmental abnormalities were 10,000 and 1,000microgl(-1), respectively. Overall, these data indicate that studies should be conducted to assess the risk of exposure of early life stages of fish to quintozene in watersheds impacted by golf courses.     

Endocrine disrupting compounds in municipal and industrial wastewater treatment plants in Northern Greece

The occurrence and fate of endocrine disrupting compounds (EDCs) in a sewage treatment plant and two industrial wastewater treatment plants from textile and tannery factories were investigated. EDCs of interest are 4-nonylphenol, 4-octylphenol, their ethoxylate oligomers (mono- and di-ethoxylates of nonylphenol and octylphenol), bisphenol A, triclosan and steroid estrogens. Target compounds were determined in dissolved fraction, total suspended solids and sludge by employing solid phase extraction and ultrasonication followed by gas chromatography–mass spectrometry.Nonylphenols and oligomers with one or two ethoxy groups were the most abundant compounds in raw wastewater as well as in effluents from all the treatment stages of sewage treatment plant, followed by triclosan and bisphenol A. Steroids were found at very low concentrations. Almost all phenolic EDCs compounds were predominantly associated to suspended solids in influents whereas the dissolved fraction dominated the treated effluents. High removal rates, ranging from 86% to 99%, were observed throughout the whole treatment process. Biodegradation was the main removal pathway of EDCs. Tannery wastewaters exhibited high concentrations of nonylphenolic compounds. This type of wastewaters could pose a significant risk to the aquatic and terrestrial environment.     

Occurrence and environmental implications of pharmaceuticals in Chinese municipal sewage sludge

The presence of pharmaceuticals in aquatic environment has become a topic of concern because of their potential adverse effects on human health and wildlife species. A total of 45 dewatered sewage sludge samples were collected throughout China and analyzed for 30 commonly consumed pharmaceutical residues. Ofloxacin was found to be the dominant contaminant with concentrations up to 24 760 μg kg⁻¹, followed by oxytetracycline (5280 μg kg⁻¹), norfloxacin (5280 μg kg⁻¹) and ketoprofen (4458 μg kg⁻¹). The concentration of pharmaceutical residues varied greatly depending on the operation conditions of wastewater treatment plants and sampling locations. Poor agreement was found between the predicted (calculation based on the annual consumption and coefficient of sludge water partition) and detected concentrations of the pharmaceuticals indicating that the occurrence of pharmaceutical residues was affected by various factors such as loading rates, sewage properties and the chemical properties such as the contribution from polar groups. National wide fate and ecotoxicity study is required for the development of control strategies.     

Assessment of the environmental fate and effects of the PPARgamma receptor agonist, pioglitazone

The environmental fate and effects of pioglitazone prescribed for the treatment of type 2 diabetes were evaluated in an environmental risk assessment following the European Medicines Agency (EMA) "Guideline on the Environmental Risk Assessment of Medicinal Products for Human Use"; EMEA/CHMP/SWP/4447/00. A predicted environment concentration (PEC) for surface water was estimated at 0.023μgL(-1), (action limit of 0.01μgL(-1)) triggering a comprehensive battery of laboratory evaluations. Pioglitazone and its major metabolites were determined not to significantly adsorb to sewage solids, were not persistent in the aquatic environment, did not bioaccumulate and were non-toxic to aquatic organisms. Pioglitazone does not pose an unacceptable risk to groundwater supplies, with concentrations not anticipated to be a risk to aquatic organisms or human drinking water supplies. Pioglitazone does not pose a risk of secondary poisoning.     

Occurrence of organic contaminants in sewage sludges from eleven wastewater treatment plants, China

This study presents the occurrence of 43 semi-volatile organic compounds (SVOCs) listed as priority pollutants by both China and the United States Environmental Protection Agency, in sewage sludges collected from eleven wastewater treatment plants (WWTPs) of mainland and Hong Kong, China. Thirty-six SVOCs were detected by gas chromatography coupled with mass spectrometer (GC-MS) and at least 14 in each sample. The most abundant compounds were phthalic acid esters (PAEs) and polycyclic aromatic hydrocarbons (PAHs) with total concentrations ranging from 10 to 114mgkg(-1) dry weight (d.w.) (with a mean of 30mgkg(-1) d.w.) and from 1.4 to 33mgkg(-1)d.w. (with a mean of 16mgkg(-1) d.w.), respectively, followed by chlorobenzenes, nitroaromatics, haloethers and halogenated hydrocarbons which occurred generally at concentrations lower than 10mgkg(-1) d.w. Large variations were observed between the concentrations of individual compounds as well as their total concentrations in sludge samples from different WWTPs. The highest values of sum concentration of 16 PAHs and of 6 PAEs were found in sewage sludge from Beijing. The mean total concentration of each class of SVOCs in sewage sludge from mainland was remarkably higher than that from Hong Kong. The concentrations of di(2-ethylhexyl) phthalate in 91% sludge samples met the limit (100mgkg(-1)d.w.) proposed by the Europe Union for land application, whereas the PAH concentrations of 64% sludge samples exceeded the maximum permissible concentration (6.0mgkg(-1)d.w.). The occurrence of SVOCs in this study are compared with other studies and their sources are discussed.     

The role of dissolved organic carbon in the mobility of Cd, Ni and Zn in sewage sludge-amended soils

A pot experiment was conducted to investigate the effect of application of naturally derived dissolved organic compounds (DOC) on the uptake of Cd, Ni and Zn by Lolium perenne L. from mixtures of soil and sewage sludge and on their extractability with CaCl2. DOC was applied at concentrations of 0, 285 and 470 mg l(-1) to a loamy sand (LS) and a sandy clay loam (SCL) soil mixed with sewage sludge at rates equivalent to 0, 10 and 50 t ha(-1). DOC applications significantly increased the extractability of metals and also their uptake by ryegrass, but the increase was greater where sludge was applied at 50 t ha(-1). It is suggested that DOC in soils significantly increased the availability of the metals to plants. This was especially the case in the LS soil, where DOC had less competition with surface sorption than in the SCL soil.