Effluent Residue Research Articles

Development of a multi-residue analytical methodology based on liquid chromatography–tandem mass spectrometry (LC–MS/MS) for screening and trace level determination of pharmaceuticals in surface and wastewaters

This paper describes development, optimization and validation of a method for the simultaneous determination of 29 multi-class pharmaceuticals using off line solid phase extraction (SPE) followed by liquid chromatography–triple quadrupole mass spectrometry (LC–MS–MS). Target compounds include analgesics and non-steroidal anti-inflammatories (NSAIDs), lipid regulators, psychiatric drugs, anti-histaminics, anti-ulcer agent, antibiotics and β-blockers. Recoveries obtained were generally higher than 60% for both surface and wastewaters, with exception of several compounds that yielded lower, but still acceptable recoveries: ranitidine (50%), sotalol (50%), famotidine (50%) and mevastatin (34%). The overall variability of the method was below 15%, for all compounds and all tested matrices. Method detection limits (MDL) varied between 1 and 30 ng/L and from 3 to 160 ng/L for surface and wastewaters, respectively. The precision of the method, calculated as relative standard deviation (R.S.D.), ranged from 0.2 to 6% and from 1 to 11% for inter and intra-day analysis, respectively. A detailed study of matrix effects was performed in order to evaluate the suitability of different calibration approaches (matrix-matched external calibration, internal calibration, extract dilution) to reduce analyte suppression or enhancement during instrumental analysis. The main advantages and drawbacks of each approach are demonstrated, justifying the selection of internal standard calibration as the most suitable approach for our study. The developed analytical method was successfully applied to the analysis of pharmaceutical residues in WWTP influents and effluents, as well as in river water. For both, river and wastewaters, the most ubiquitous compounds belonged to the group of anti-inflammatories and analgesics, antibiotics, the lipid regulators being acetaminophen, trimethoprim, ibuprofen, ketoprofen, atenolol, propranolol, mevastatin, carbamazepine and ranitidine the most frequently detected compounds.

Effects of Dissolved Organic Matter on Permethrin Bioavailability to Daphnia Species

Synthetic pyrethroids are widely used insecticides in both agricultural and urban environments. Recent studies show frequent appearances of pyrethroid residues in runoff effluents and sediments, which stimulated concerns over the potential ecotoxicological implications. Pyrethroids are known to have two contrasting characteristics, high aquatic toxicity and strong affinity for the solid phase, that may negate the actual toxicity in a multiphased system. This study evaluated the effect of dissolved organic matter (DOM) on the pyrethroid uptake by and acute toxicity to water-column invertebrates using permethrin as a model compound. During the bioassays, the freely dissolved permethrin concentration was simultaneously measured using poly(dimethylsiloxane) (PDMS) fibers as a biomimetic surrogate. The presence of DOM consistently decreased permethrin uptake and increased its LC(50). For instance, compared to the DOM-free treatment, the LC(50) of permethrin to Ceriodaphnia dubia in a pond water containing DOM at 10 mg L(-)(1) increased from 0.56 to 1.03 microg L(-)(1), whereas the bioaccumulation factor by Daphnia magna decreased by 56%. Permethrin accumulation on the PDMS fiber closely mimicked permethrin uptake by D. magna. Statistical analyses suggest that permethrin associated with DOM was completely unavailable to D. magna or C. dubia. The effect of DOM on permethrin bioavailability appeared to depend also on the source of the DOM. These results indicate that the inhibitory role of DOM should be considered in the development of toxicologically relevant water quality limits and in monitoring protocols for permethrin and other pyrethroids in runoff effluents and surface streams that ubiquitously contain DOM.

Environmental risk assessment of pharmaceutical residues in wastewater effluents, surface waters and sediments

Pharmaceutical residues in the environment, and their potential toxic effects, have been recognized as one of the emerging research area in the environmental chemistry. The increasing attention, on pharmaceutical residues as potential pollutants, is due that they often have similar physico-chemical behaviour than other harmful xenobiotics which are persistent or produce adverse effects. In addition, by contrast with regulated pollutants, which often have longer environmental half-lives, its continuous introduction in the environment may make them “pseudopersistents”. Pharmaceutical residues and/or their metabolites are usually detected in the environment at trace levels, but, even that, low concentration levels (ng/L or μg/L) can induce to toxic effects. In particular, this is the case of antibiotics and steroids that cause resistance in natural bacterial populations or endocrine disruption effects. In this study, an overview of the environmental occurrence and ecological risk assessment of pharmaceutical residues is presented from literature data. Risk Quotient method (RQ) was applied as a novel approach to estimate the environmental risk of pharmaceuticals that are most frequently detected in wastewater effluents, surface waters and sediments.

Residues and source identification of persistent organic pollutants in farmland soils irrigated by effluents from biological treatment plants

Sewage and industrial effluents from biological treatment plant have been widely used for agricultural irrigation in north part of China. However, effluents after biological treatment still contain heavy metals and persistent organic contaminants. The persistent organic contaminants accumulated in soil may transfer through the food chains and cause adverse health effects on human or biological effects on soil fauna and flora after long-term application. In present study, field surveys were carried out in the farmlands irrigated by effluents from biological treatment plants that receive sewage wastewater and industrial discharges. Residues of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) in the soils irrigated using both ground water and effluents were compared. The origins of PAHs in the soils were discussed. The results showed that wastewater irrigation could cause accumulation of PAHs in soils close to the pollution discharge. Significantly higher concentrations of PAHs were observed in the sampling sites close to the entrance of main channel in contrast to those along branches and the reference sites. There was no significant relationship between the accumulation of persistent organic pollutants and organic matter content in soil (TOC). Soil contamination of these persistent organic pollutants as affected by effluent irrigation was characterized by the dominant accumulation of high-molecular-weight PAHs (HMW-PAHs). In the case study, concentration of benzo[ a]pyrane (BaP, 45.6 ng/g), indeno[1,2,3- cd]pyrene (IcP, 86.3 ng/g), benzo[ g,h,i]perlene (BgP, 66.9 ng/g) could exceed the limits of the soil quality standard for biodegraded soils. In identification of the sources, the IcP/BgP values of PAHs in soils were more close to that in air particulates from coal/coke source (1.09 ± 0.03 ng/g) [Dickhut RM, Canuel EA, Gustafson KE, Liu K, Arzayus KM, Walkers E, et al. Automotive sources of carcinogenic polycyclic aromatic hydrocarbons associated with particulate matter in the chesapeake bay region. Environ Sci Technol 2000;34:4635–40]. Therefore, both of the PAHs residues in effluents and emission from a nearby coal/coke plant were responsible. Also in this case study, low levels of the OCPs were observed and were not of significant concern in this wastewater irrigation area. Among the different OCPs analyzed, DDTs (mean 8.41 ng/g) and HCHs (mean 2.91 ng/g) were the major components. From the ratios of DDT/DDTs and β -HCH/HCHs, it indicated that OCPs residues should be from historical usage.

Comparison of microbial markers (15N and purine bases) and bacterial isolates for the estimation of rumen microbial protein synthesis

AbstractThe first objective of this experiment was to investigate the effect of using different bacterial isolates on the estimation of microbial protein production in semi-continuous fermenters (RUSITEC) given four diets, and to test whether a ‘mixed’ bacterial pellet was representative of the whole bacterial population in the fermenters. A second objective was to compare two different microbial markers (nitrogen-fifteen (15N) and purine bases (PB)). Diets consisted of neutral-detergent fibre from grass hay (10 g/day) and sugar-beet pulp (2 g/day) and 280 mg/day of one of four N forms (isolated soya-bean protein, soya-bean peptides, amino acids blended to profile soya-bean protein and NH4Cl). Two 14-day incubation runs were carried out and in each run each of the four different diets were given to two vessels. On days 12 and 13, total digesta (effluent plus nylon bags residues) was collected for analyses of non-ammonia N,15N enrichment and PB concentration, and for isolation of total mixed bacterial pellets (TB). On the last day of each incubation run, the system was stopped for isolation of liquid- (LAB) and solid-associated (SAB) bacteria. Microbial N flow was estimated from the15N enrichment and PB concentration in both total digesta and in the three different bacterial pellets (TB, LAB, and SAB). For all diets, LAB presented a greater (P < 005)15N enrichment and PB: N ratio than SAB, with TB having an intermediate value. For both markers, the use of LAB produced the lowest (P < 005) estimates of microbial N flow and the use of SAB produced the greatest (P < 005) estimates. The use of TB produced intermediate values with all diets, suggesting that TB consisted of SAB and LAB. For all bacterial pellets, PB produced greater (P 005) values of microbial N flow than15N. However, there was a positive relationship (r = 0·883; P 0001; no. = 15) between the values of microbial N flow determined with the two markers when TB were used as reference.

Contraceptive pill residues in sewage effluent are estrogenic to fish

The estrogenicity of sewage effluent water to fish has been described in several countries. Natural oestrogens have been confirmed as major causing agents in several British rivers. In a recent study (Larsson et al., Aquatic Toxicology, 1999, 91–97) we identified estrogenic substances by GC/MS in effluent water from a Swedish sewage treatment works receiving mainly domestic wastewater. Substances found include the synthetic estrogen used in contraceptives 17α-ethinylestradiol (4.5 ng/l), the natural estrogens estrone (5.8 ng/l) and 17β-estradiol (1.1 ng/l) and the weaker non-steroidal estrogens 4-nonylphenol (840 ng/l) and bisphenol A (490 ng/l). Ethinylestradiol exceeded levels shown to be estrogenic to fish by 45 times. The estrogenicity of the effluent water was investigated by introducing juvenile rainbow trout ( Oncorhynchus mykiss) in cages downstream of the sewage treatment works. All estrogens indicated above were present in the bile of the fish, and the estrogen-inducible protein, vitellogenin, was found in large amounts in the plasma as determined by ELISA and Western blotting. At present we are studying effects further downstream on caged as well as wildcaught fish. Our studies suggest that a widely used synthetic estrogen affects the endocrine systems of fish exposed to sewage effluent water.

Monitoring of diester cationic surfactant residues in UK and Dutch sewage treatment effluents

Monitoring of diester cationic surfactant residues in UK and Dutch sewage treatment effluents

Promising Approaches to Recycling Effluent Residues from Galvanizing Operations

Promising Approaches to Recycling Effluent Residues from Galvanizing Operations

Identification of organic residues in tertiary effluents by GC/EI-MS, GC/CI-MS and GC/TSQ-MS

A method was developed for the analysis of non-volatile dissolved organic residues in tertiary treated wastewater effluents. This method involved concentration of samples by rotary evaporation, propylation using propanol/formic acid/acetyl chloride, and separation, detection and quantitation by capillary GC/EI and CI-MS and GC/TSQ-MS analysis. Ethylenediamine tetraacetic acid (EDTA) was the most prominent compound found in both granular activated carbon (GAC) and chlorinated GAC effluents (110 and 140 μg/L, respectively). Other compounds identified included nitrilotriacetic acid (NTA), carboxyalkylphenoxy ethoxy carboxylates, poly(propoxy), poly(ethoxy) or poly(ethoxy)(propoxy) compounds, small aliphatic dicarboxylic acids and aldehydes, all at lg/L levels. Approximately 80% of all chromatographically separated compounds were positively or tentatively identified. The identified compounds are estimated to account for approximately 10% of the dissolved organic carbon.

Irrigation of bananas with secondary treated sewage effluent. II. Effect on plant nutrients, additional elements and pesticide residues in plants, soil and leachate using drainage lysimeters

The effects of irrigating banana plants with secondary treated sewage effluent were examined using lysimeters at Woolgoolga, N.S.W. Lysimeters were sheltered from rain so that they received only effluent or tap water without substantial leaching occurring. Total application was c. 4700 mm over c. 30 months, equivalent to about 8 years field requirements for supplementary irrigation. At the end of the growth period, plants and soils were analysed for a wide range of chemical parameters. Soil profiles were then leached and the collected leachate was also analysed. Irrigation with effluent had no effect on plant size. Plants watered with effluent contained 225% more sodium, 81% more boron, 43% more copper, 26% more chloride, and about 16% more nitrogen, phosphorus, potassium and magnesium than plants watered with tap water. Soils watered with effluent accumulated more phosphorus, sulfate, chloride, calcium and sodium than soils watered with tap water. Phosphorus sorption results indicated that it would take over 200 years of supplementary watering with effluent to saturate the profile with P. Leachate collected after the growth period from lysimeters watered with effluent contained negligible phosphorus, but considerable sodium, chloride, sulfate, and magnesium. There was no evidence of sodium in effluent displacing calcium from the profile. The high concentration of magnesium in leachate from both treatments indicated that magnesium was displaced by the high levels of potassium fertilizer applied to ensure adequacy for growth of banana plants. Boron concentrations in the leachate indicated that boron would not accumulate in the profile under natural rainfall conditions. Other trace elements were also most unlikely to accumulate to problem levels. Pesticide residue testing of banana pulp, soils and leachate indicated minimal likelihood of problems associated with such residues in local effluent. It was concluded that supplementary irrigation of bananas with the effluent tested was unlikely to cause any problems with either soil or plant chemistry, given the considerable surplus of rainfall which occurs locally in most autumns.

Container residue after the administration of aqueous activated charcoal products

Commercial aqueous activated charcoal (AC) products may sit in emergency departments, pharmacies, and homes for prolonged periods resulting in the inability to resuspend the AC for patient administration. The potential risk to the patient from not receiving an adequate amount of AC, especially when AC may be the sole means of gastric decontamination, is obvious. To simulate this potential problem, samples of five different aqueous AC products (ActaChar, Actidose, InstaChar, LiquiChar, and SuperChar) were placed into storage for periods of 3 and 12 months. At the end of each study period, samples were agitated and the effluent and container residue were collected, oven-dried, and weighed. With the exception of Actidose, all products retained substantial amounts of AC in the container at both time intervals. These data stress the negative impact of dormant storage on the resuspendability of aqueous activated charcoal products. Furthermore, they suggest the importance of thorough container agitation and rinsing to insure that the patient receives sufficient AC. This is especially important when AC is the sole means of decontamination.

Advances in the Afterchrome Dyeing of Wool

Recommendations are outlined for the afterchrome dyeing of wool to give minimum chrome residues in dyehouse effluent and minimum wool damage. Particular reference is made to the use of a new product Lyocol CR, which reduces chrome residues in exhausted dye liquors and ensures efficient utilisation of minimum chrome additions, thus giving good wet fastness. Low‐chrome methods permit the wider use of chrome dyes for machine‐washable wool and new dyes which increase the shade gamut available are discussed.

Vacuum filtration and centrifugal dewatering of materials extracted from drainage in refractory plants

With vacuum filtration the following apply: For dewatering the effluent (drainage) residue the concentration of the original suspension should be not less than 700 g/liter. The suction method can be used to dewater only residues based on chamotte dust or mixtures of chamotte and clay (not more than 20%); on the drum vacuum filter even with a mixture of chamotte and clay (not more than 20%) we obtain unsatisfactory results. To dewater suspensions containing chamotte and clay dust it is possible to use vacuum-filters with a residue feed using the overflow method, but such vacuum-filters are not being made by Soviet industry. Vacuum filtration as a method of dewatering residues from drainage contaminated with chamotte and clay is not recommended. Using centrifuging: The residues of the effluents can be dewatered on centrifuges; it is best to dewater residues formed from the coagulation of drainage water than residues formed from noncoagulated drainage. Centrifuging is affected by the nature of the formation of the original material. It is necessary to continue the research into laboratory and production centrifuges.

A general method for the determination of organophosphorus pesticide residues in river waters and effluents by gas, thin-layer and gel chromatography.

A general, comprehensive scheme for the extraction of organophosphorus pesticides from river waters and sewage effluents is described. The pesticides, after extraction with chloroform, are determined by gas and thin-layer chromatography. The procedure includes details of an improvement that enables all of the pesticides to be detected on thin-layer chromatoplates with a phosphorus-specific ammonium molybdate spray. The use of gel chromatography on columns of Sephadex LH 20 as an adjunct to identification is also described.