Reviews - Surface Water - Groundwater - Biodegradation - Photolysis - Sorption - Biological Impacts - Other


Review Papers on PPCP in Natural Systems
Citation Notes Abstract
Mompelat, S., Le Bot, B. and Thomas, O. (2009) Occurrence and fate of pharmaceutical products and by-products, from resource to drinking water. Environment International 35(5), 803-814.
  Among all emerging substances in water, pharmaceutical products (PPs) and residues are a lot of concern. These last two years, the number of studies has increased drastically, however much less for water resources and drinking water than for wastewater. This literature review based on recent works, deals with water resources (surface or groundwater), focusing on characteristics, occurrence and fate of numerous PPs studied, and drinking water including water quality. Through this review, it appears that the pharmaceutical risk must be considered even in drinking water where concentrations are very low. Moreover, there is a lack of research for by-products (metabolites and transformation products) characterization, occurrence and fate in all water types and especially in drinking water.


PPCPs in Surface Waters: Observations and Models
Citation Notes Abstract
Sengupta, A., Lyons, J.M., Smith, D.J., Drewes, J.E., Snyder, S.A., Heil, A. and Maruya, K.A. (2013) The Occurrence and Fate of Chemicals of Emerging Concern in Coastal Urban Rivers Receiving Discharge of Treated Municipal Wastewater Effluent. Environmental Toxicology and Chemistry 33(2), 350-358.
little loss in urban river; see 697z L#18 To inform future monitoring and assessment of chemicals of emerging concern (CECs) in coastal urban watersheds, the occurrence and fate of more than 60 pharmaceuticals and personal care products (PPCPs), commercial/household chemicals, current-use pesticides, and hormones were characterized in 2 effluent-dominated rivers in southern California (USA). Water samples were collected during 2 low-flow events at locations above and below the discharge points of water reclamation plants (WRPs) and analyzed using gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry. Approximately 50% of targeted CECs were detectable at stations downstream from WRPs, compared with <31% and <10% at the reference stations above the WRPs. Concentrations of chlorinated phosphate flame retardants were highest among the CECs tested, with mean total aggregate concentrations of tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), and tris(1,3-dichloro-2-propyl) phosphate (TDCPP) of 3400ng/L and 2400ng/L for the 2 rivers. Maximum in-stream concentrations of pyrethroids (bifenthrin and permethrin), diclofenac, and galaxolide exceeded risk-based thresholds established for monitoring of CECs in effluent-dominated receiving waters. In contrast, maximum concentrations of PPCPs commonly detected in treated wastewater (e.g., acetaminophen, N,N,diethyl-meta-toluamide [DEET], and gemfibrozil) were less than 10% of established thresholds. Attenuation of target CECs was not observed downstream of WRP discharge until dilution by seawater occurred in the tidal zone, partly because of the short hydraulic residence times in these highly channelized systems (<3 d). In addition to confirming CECs for future in-stream monitoring, these results suggest that conservative mass transport is an important boundary condition for assessment of the input, fate, and effects of CECs in estuaries at the bottom of these watersheds.
Jurgens, M.D., Holthaus, K.I.E., Johnson, A.C., Smith, J.J.L., Hetheridge, M. and Williams, R.J. (2002) The potential for estradiol and ethinylestradiol degradation in English rivers. Environmental Toxicology and Chemistry 21(3), 480-488. kinetics of estrogen loss: see 697z L#18 Water samples were collected in spring, summer, and winter from English rivers in urban/industrial (River Aire and River Calder, Yorkshire, UK) and rural environments (River Thames, Oxfordshire, UK) to study the biodegradation potential of the key steroid estrogen 17beta-estradiol (E2) and its synthetic derivate ethinylestradiol (EE2). Microorganisms in the river water samples were capable of transforming E2 to estrone (E1) with half-lives of 0.2 to 9 d when incubated at 20degreesC. The E1 was then further degraded at similar rates. The most rapid biodegradation rates were associated with the downstream summer samples of the River Aire and River Calder. E2 degradation rates were similar for spiking concentrations throughout the range of 20 ng/L to 500 mug/L. Microbial cleavage of the steroid ring system was demonstrated by release of radiolabeled CO2 from the aromatic ring of E2 (position 4). When E2 was degraded, the loss of estrogenicity, measured by the yeast estrogen screen (YES) assay, closely followed the loss of the parent molecule. Thus, apart from the transient formation of E1, the degradation of E2 dues not form other significantly estrogenic intermediates. The E2 could also be degraded when incubated with anaerobic bed sediments. Compared to E2, EE2 was much more resistant to biodegradation, but both E2 and EE2 were susceptible to photodegradation, with half-lives in the order of 10 d under ideal conditions.



PPCPs in Groundwaters: Observations and Models
(see also: Water Treatment-Riverbank Filtration)
Citation Notes Abstract
Laws, B.V., Dickenson, E.R.V., Johnson, T.A., Snyder, S.A. and Drewes, J.E. (2011) Attenuation of contaminants of emerging concern during surface-spreading aquifer recharge. Science of the Total Environment 409(6), 1087-1094.   The attenuation of a diverse suite of contaminants of emerging concern (CECs) and bulk water quality changes was evaluated at a surface-spreading aquifer recharge operation across a detailed subsurface profile (9 locations), representing both short- and long-travel times (10 h to 60 days). Seventeen CECs were detected in the recharge basin and the concentrations of all were reduced during soil aquifer treatment (SAT), with 11 of the target compounds attenuated by >80% after 60 days of travel time. Select CECs (atenolol, gemfibrozil, N,N-diethly-3-methylbenzamide, meprobamate, tris(2-chloroethyl)phosphate, and primidone) and bulk water organic-carbon measurements (total organic carbon, biodegradable organic carbon, size-exclusion chromatography and fluorescence excitation-emission matrices) were identified as monitoring parameters that can be used to assess SAT performance at surface-spreading operations.
Van Stempvoort, D.R., Robertson, W.D. and Brown, S.J. (2011) Artificial Sweeteners in a Large Septic Plume. Ground Water Monitoring and Remediation 31(4), 95-102.   Four artificial sweeteners, acesulfame, sucralose, cyclamate, and saccharin were detected in a large septic plume at Long Point, Ontario, Canada. The pattern of sweetener detections in the groundwater indicated that they were derived from waste water seepage from a large septic system at the site. Acesulfame was pervasive in the septic plume, whereas the other three sweeteners have been attenuated, probably by microbial degradation.
Rauch-Williams, T., Hoppe-Jones, C. and Drewes, J.E. (2010) The role of organic matter in the removal of emerging trace organic chemicals during managed aquifer recharge. Water Research 44(2), 449-460.   This study explored the effect of different bulk organic carbon matrices on the fate of trace organic chemicals (TOrC) during managed aquifer recharge (MAR) infiltration through porous media was simulated in biologically active column experiments under aerobic and anoxic recharge conditions. Wastewater effluent derived organic carbon types, differing in hydrophobicity and biodegradability (i e, hydrophobic acids, hydrophilic carbon, organic colloids), were used as feed substrates in the column experiments. These carbon substrates while fed at the same concentration differed in their ability to support soil biomass growth during porous media infiltration Removal of degradable TOrC (with the exception of diclofenac and propyphenazone) was equal or better under aerobic versus anoxic porous media infiltration conditions During the initial phase of infiltration, the presence of biodegradable organic carbon (BDOC) enhanced the decay of degradable TOrC by promoting soil biomass growth, suggesting that BDOC served as a co-substrate in a co-metabolic transformation of these contaminants However, unexpected high removal efficiencies were observed for all degradable TOrC in the presence of low BDOC concentrations under well adopted oligotrophic conditions It is hypothesized that removal under these conditions is caused by a specialized microbial community growing on refractory carbon substrates such as hydrophobic acids Findings of this study reveal that the concentration and character of bulk organic carbon present in effluents affect the degradation efficiency for TOrC during recharge operation Specifically aerobic, oligotrophic microbiological soil environments present favorable conditions for the transformation of TOrC, including rather recalcitrant compounds such as chlorinated flame retardants


Biodegradation of PPCPs
Citation Notes Abstract


Photolysis of PPCPs
Citation Notes Abstract

Sorption of PPCPs
Citation Notes Abstract
Pan, B. and Xing, B. (2011) Pharmaceuticals and Personal Care Products in Soils and Sediments, In Biophysico-Chemical Processes of Anthropogenic Organic Compounds in Environmental Systems. Xing, B., Senesi, N. and Huang, P.M. (eds), pp. 185-213, Wiley, Hoboken, NJ.   This chapter covers occurrence of PPCPs in soils and sediments (7.2), interactions between PPCPs and soil/sediment components (organic matter and inorganic fractions; 7.3 & 7.4), effect of solution chemistry on PPCP sorption (7.5), effect of PPCP sorption on PPCP degradation and leaching (7.6 & 7.7), models for prediction of PPCP soprtion in soils/sediments with an emphasis on departure from traditional models for the environmental behavior of hydrophobic organic contaminants, and summary of the overall approaches and perspectives regarding soils/sediment-PPCP interactions.
Williams, M., Ong, P.L., Williams, D.B. and Kookana, R.S. (2009) Estimating the Sorption of Pharmaceuticals Based on their Pharmacological Distribution. Environmental Toxicology and Chemistry 28(12), 2572-2579.

  Pharmaceuticals released into aquatic systems are expected to sorb to sediments to varying degrees. Their sorption is likely to influence their fate and, ultimately, the risk they pose to aquatic organisms. This has led to the European Medicines Agency requiring an assessment of affinity to solids, using batch sorption methods, for the environmental risk assessment (ERA) of new human medicines. However, a large body of data is generated before pharmaceuticals are released onto the market, including their extent of distribution throughout the human body, measured by the volume of distribution (VD). In the present study, batch sorption experiments were undertaken using 12 different soils and sediments to determine whether VD was a good indicator of experimental K-d values for 21 pharmaceuticals. The r(2) values obtained from the regressions ranged from 0.39 to 0.76 (with a median value of 0.5) and all regressions were found to be significant. The use of this more comprehensive set of soils and sediments was consistent with previous studies comparing VD and Kd, despite the Kd values of the selected pharmaceuticals varying greatly between soils. The relationship between Kd and VD was greatly improved when zwitterionic antibiotics and carbamazepine were not included, possibly due to complex sorption or pharmacokinetic behavior. There are likely to be a number of factors affecting the sorption of pharmaceuticals that cannot be explained by VD. However, further work may elucidate how these factors can be accounted for, enabling VD to be effectively used to facilitate the ERA of human pharmaceuticals with already available information.
Stevens-Garmon, J., Drewes, J.E., Khan, S.J., McDonald, J.A. and Dickenson, E.R.V. (2011) Sorption of emerging trace organic compounds onto wastewater sludge solids. Water Research 45(11), 3417-3426.   This work examined the sorption potential to wastewater primary- and activated-sludge solids for 34 emerging trace organic chemicals at environmentally relevant concentrations. These compounds represent a diverse range of physical and chemical properties, such as hydrophobicity and charge state, and a diverse range of classes, including steroidal hormones, pharmaceutically-active compounds, personal care products, and household chemicals. Solid-water partitioning coefficients (K(d)) were measured where 19 chemicals did not have previously reported values. Sludge solids were inactivated by a nonchemical lyophilization and dry-heat technique, which provided similar sorption behavior for recalcitrant compounds as compared to fresh activated-sludge. Sorption behavior was similar between primary- and activated-sludge solids from the same plant and between activated-sludge solids from two nitrified processes from different wastewater treatment systems. Positively-charged pharmaceutically-active compounds, amitriptyline, clozapine, verapamil, risperidone, and hydroxyzine, had the highest sorption potential, log K(d) = 2.8-3.8 as compared to the neutral and negatively-charged chemicals. Sorption potentials correlated with a compound's hydrophobicity, however the higher sorption potentials observed for positively-charged compounds for a given log D(ow) indicate additional sorption mechanisms, such as electrostatic interactions, are important for these compounds. Previously published soil-based one-parameter models for predicting sorption from hydrophobicity (log K(ow) > 2) can be used to predict sorption for emerging nonionic compounds to wastewater sludge solids.


Biologial Impacts
Citation Notes Abstract
Wiklund, A.K.E., Breitholtz, M., Bengtsson, B.E. and Adolfsson-Erici, M. (2012) Sucralose - An ecotoxicological challenger? Chemosphere 86(1), 50-55.   The non-calorie sweetener sucralose - sucrose containing three chlorine atoms - is intensively sweet and has become a popular substitute for sugar. Its widespread use, exceptional stability in combination with high water solubility have thus resulted in contamination of recipient waters. Earlier studies on sucralose in aquatic organisms indicate low bioaccumulation potential and negligible acute/chronic toxicity, but the close structural resemblance with sucrose in combination with the importance of sugar in nature, warrant a more detailed ecotoxicological assessment. The aim of this investigation was therefore to study behavioural and physiological effects of sucralose in crustaceans. Our results show that both physiology and locomotion behaviour were affected by exposure to sucralose. In Daphnia magna, the behavioural response was manifested as altered swimming height and increased swimming speed, whereas in gammarids the time to reach food and shelter was prolonged. Regardless if these behavioural responses were initiated via traditional toxic mechanisms or stimulatory effects, they should be considered as a warning, since exposed organisms may diverge from normal behaviour, which ultimately can have ecological consequences.
Sanchez, W., Sremski, W., Piccini, B., Palluel, O., Maillot-Marechal, E., Betoulle, S., Jaffal, A., Ait-Aissa, S., Brion, F., Thybaud, E., Hinfray, N. and Porcher, J.M. (2011) Adverse effects in wild fish living downstream from pharmaceutical manufacture discharges. Environment International 37(8), 1342-1348.   A set of biochemical and histological responses was measured in wild gudgeon collected upstream and downstream of urban and pharmaceutical manufacture effluents. These individual end-points were associated to fish assemblage characterisation. Responses of biotransformation enzymes, neurotoxicity and endocrine disruption biomarkers revealed contamination of investigated stream by a mixture of pollutants. Fish from sampled sites downstream of the industrial effluent exhibited also strong signs of endocrine disruption including vitellogenin induction, intersex and male-biased sex-ratio. These individual effects were associated to a decrease of density and a lack of sensitive fish species. This evidence supports the hypothesis that pharmaceutical compounds discharged in stream are involved in recorded endocrine disruption effects and fish population disturbances and threaten disappearance of resident fish species. Overall, this study gives argument for the utilisation of an effect-based monitoring approach to assess impacts of pharmaceutical manufacture discharges on wild fish populations.


Large PPCP Studies with some Natural Systems Data
Citation Notes Abstract