Occurrence of pharmaceuticals and personal care products and associated environmental risks in the central and lower Yangtze river, China.

Pharmaceutical and personal care products (PPCPs) residues are being highlighted around the world as of emerging concern in surface waters. Here the occurrence of PPCPs in the central and lower Yangtze River, along with four large freshwater lakes within the river basin (Dongting, Poyang, Tai, and Chao) was reported. Fifteen out of twenty selected PPCPs were detected in the collected surface water samples. Caffeine, paraxanthine, sulfamethazine, and clindamycin were detected with 100 percent frequency in the Yangtze River. In the river, the highest average concentration was observed for erythromycin (296 ng L(-1)), followed by caffeine (142 ng L(-1)) and paraxanthine (41 ng L(-1)). In the four lakes, total PPCP concentrations were much higher in the Chao (1547 ng L(-1)) and Tai (1087 ng L(-1)) lakes compared to the Poyang (108 ng L(-1)) and Dongting (137 ng L(-1)) lakes. Lincomycin and clindamycin were most abundant in the lakes, especially in the Tai Lake. Environmental risk assessment for the worst case scenario was assessed using calculated risk quotients, and indicates a high environmental risk of erythromycin and clarithromycin in the Yangtze River, clarithromycin in the Chao Lake, and clindamycin in the Tai Lake.

Transfer of wastewater associated pharmaceuticals and personal care products to crop plants from biosolids treated soil.

The plant uptake of emerging organic contaminants such as pharmaceuticals and personal care products (PPCPs) is receiving increased attention. Biosolids from municipal wastewater treatment have been previously identified as a major source for PPCPs. Thus, plant uptake of PPCPs from biosolids applied soils needs to be understood. In the present study, the uptake of carbamazepine, diphenhydramine, and triclocarban by five vegetable crop plants was examined in a field experiment. At the time of harvest, three compounds were detected in all plants grown in biosolids-treated soils. Calculated root concentration factor (RCF) and shoot concentration factor (SCF) are the highest for carbamazepine followed by triclocarban and diphenhydramine. Positive correlation between RCF and root lipid content was observed for carbamazepine but not for diphenhydramine and triclocarban. The results demonstrate the ability of crop plants to accumulate PPCPs from contaminated soils. The plant uptake processes of PPCPs are likely affected by their physico-chemical properties, and their interaction with soil. The difference uptake behavior between plant species could not solely be attributed to the root lipid content.

Reconnaissance of selected PPCP compounds in Costa Rican surface waters.

Eighty-six water samples were collected in early 2009 from Costa Rican surface water and coastal locations for the analysis of 34 pharmaceutical and personal care product compounds (PPCPs). Sampling sites included areas receiving treated and untreated wastewaters, and urban and rural runoff. PPCPs were analyzed using a combination of solid phase extraction and liquid chromatography tandem mass spectrometry. The five most frequently detected compounds were doxycycline (77%), sulfadimethoxine (43%), salicylic acid (41%), triclosan (34%) and caffeine (29%). Caffeine had the maximum concentration of 1.1 mg L(-1), possibly due to coffee bean production facilities upstream. Other compounds found in high concentrations include: doxycycline (74 µg L(-1)), ibuprofen (37 µg L(-1)), gemfibrozil (17 µg L(-1)), acetominophen (13 µg L(-1)) and ketoprofen (10 µg L(-1)). The wastewater effluent collected from an oxidation pond had similar detection and concentrations of compounds compared to other studies reported in the literature. Waters receiving runoff from a nearby hospital showed higher concentrations than other areas for many PPCPs. Both caffeine and carbamazepine were found in low frequency compared to other studies, likely due to enhanced degradation and low usage, respectively. Overall concentrations of PPCPs in surface waters of Costa Rica are inline with currently reported occurrence data from around the world, with the exception of doxycycline.

Uptake of pharmaceutical and personal care products by soybean plants from soils applied with biosolids and irrigated with contaminated water.

Many pharmaceuticals and personal care products (PPCPs) are commonly found in biosolids and effluents from wastewater treatment plants. Land application of these biosolids and the reclamation of treated wastewater can transfer those PPCPs into the terrestrial and aquatic environments, giving rise to potential accumulation in plants. In this work, a greenhouse experiment was used to study the uptake of three pharmaceuticals (carbamazepine, diphenhydramine, and fluoxetine) and two personal care products (triclosan and triclocarban) by an agriculturally important species, soybean (Glycine max (L.) Merr.). Two treatments simulating biosolids application and wastewater irrigation were investigated. After growing for 60 and 110 days, plant tissues and soils were analyzed for target compounds. Carbamazepine, triclosan, and triclocarban were found to be concentrated in root tissues and translocated into above ground parts including beans, whereas accumulation and translocation for diphenhydramine and fluoxetine was limited. The uptake of selected compounds differed by treatment, with biosolids application resulting in higher plant concentrations, likely due to higher loading. However, compounds introduced by irrigation appeared to be more available for uptake and translocation. Degradation is the main mechanism for the dissipation of selected compounds in biosolids applied soils, and the presence of soybean plants had no significant effect on sorption. Data from two different harvests suggest that the uptake from soil to root and translocation from root to leaf may be rate limited for triclosan and triclocarban and metabolism may occur within the plant for carbamazepine.

Dissipation and leaching potential of selected pharmaceutically active compounds in soils amended with biosolids.

Biosolids land application is an important pathway introducing pharmaceuticals into the environment. In this work, laboratory column and dissipation experiments were performed using soils of varying properties in order to study the fate and transport of pharmaceutical residues introduced by the land application of biosolids. For experimentation, five pharmaceutical compounds (carbamazepine, diphenhydramine, fluoxetine, diltiazem, and clindamycin) and two metabolites (carbamazepine-10,11-epoxide and norfluoxetine) commonly found in biosolids were selected. Leaching experiments indicate that the selected pharmaceuticals have low mobility in tested soils. However, small portions of the applied pharmaceuticals were recovered in the leachates, likely attributed to sorption to dissolved organic matter. Dissipation experiments show that carbamazepine, diphenhydramine, and fluoxetine were persistent in soils, whereas the dissipation of diltiazem and clindamycin was affected by redox conditions and soil properties.

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 microg 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.

Adsorption and degradation of triclosan and triclocarban in soils and biosolids-amended soils.

Triclosan and triclocarban are antibacterial agents that are widely used in numerous personal care products. Limited information is available on their environmental behavior in soils and soils land applied with wastewaters and biosolids. In this study, laboratory experiments were performed to investigate their adsorption and degradation in soils. Both antibacterial agents adsorbed strongly to the sandy loam and silty clay soils with and without addition of biosolids, with distribution coefficients (K(d)) ranging from 178 to 264 L kg(-1) for triclosan and from 763 to 1187 L kg(-1) for triclocarban. Sorption of triclosan decreased with increase in soil pH from 4 to 8, whereas triclocarban sorption showed no effect within the tested pH range. Competitive sorption was observed when triclosan and triclocarban coexisted, but the cosolute effect was concentration dependent. Biosolids amendment increased the sorption of triclosan and triclocarban, likely due to the addition of soil organic matter, but displayed no significant effect on degradation.

Mapping the total phosphorus concentration of biosolid amended surface soils using LANDSAT TM data.

Conventional methods for soil sampling and analysis for soil variability in chemical characteristics are too time-consuming and expensive for multi-seasonal monitoring over large-scale areas. Hence, the objectives of this study are: 1) to determine changes in chemical concentrations of soils that are amended with treated sewage sludge; and 2) to determine if LANDSAT TM data can be used to map surface chemical characteristics of such amended soils. For this study, we selected two fields in NW Ohio, designated as F34 and F11, that had been applied with 34 and 11 ton acre(-1) of biosolids, respectively. Soil samples from a total of 70 sampling locations across the two fields were collected one day prior to LANDSAT 5 overpass and were analyzed for several elemental concentrations. The accumulation of Ba, Cd, Cu, S and P were found to be significantly higher in the surface soils of field F34, compared to field F11. Regression equations were established to search for algorithms that could map these five elemental concentrations in the surface soils using six, dark-object-subtracted (DOS) LANDSAT TM bands and the 15 non-reciprocal spectral ratios derived from these six bands for the May 20, 2005, LANDSAT 5 TM image. Phosphorus (P) had the highest R(2) adjusted value (67.9%) among all five elements considered, and the resulting algorithm employed only spectral ratios. This model was successfully tested for robustness by applying it to another LANDSAT TM image obtained on June 5, 2005. Our results enabled us to conclude that LANDSAT TM imagery of bare-soil fields can be used to quantify and map the spatial variation of total phosphorous concentration in surface soils. This research has significant implications for identification and mapping of areas with high P, which is important for implementing and monitoring the best phosphorous management practices across the region.

Sorption and biodegradation of selected antibiotics in biosolids.

Laboratory experiments were conducted to investigate the sorption and degradation of six antibiotics including Ciprofloxacin (CIP), Tetracycline (TC), Doxycycline (DTC), Sulfamethazine (SMZ), Sulfamethoxazole (SMX) and Clindamycin (CLD) in an aerobically digested biosolid. In the sorption experiment, CIP, TC, and DTC sorbed strongly, followed by CLD, while SMZ and SMX were only weakly sorbed to particles. An adsorption/desorption hysteresis was observed for nearly all the antibiotics to some extent. In the degradation experiment, the elimination of antibiotics, except CIP for which no degradation was observed, was found primarily attributed to biological degradation. For the degradation of TC, DTC, and CLD, a stable phase was achieved after preliminary degradation. We hypothesize that the nondegradable residuals are nondesorbable portions of sorbed antibiotics. From the results, other than SMX, all tested antibiotics can potentially survive biosolids storage periods and can be introduced into the environment following biosolids land application.

Determination of the persistence of pharmaceuticals in biosolids using liquid-chromatography tandem mass spectrometry.

Sludge generated in waste water treatment process can be a major sink for some pharmaceutical and personal care products (PPCPs). The land application of sewage sludge (in the form of biosolids in the United States) can therefore potentially introduce PPCPs into the environment. After treatment, biosolids are often subjected to a storage period before land application. However, little information is available with regard to the fate of PPCPs in biosolids during the storage. In this work, the persistence of seven pharmaceuticals and one antibacterial was evaluated using ultrasonic extraction and liquid-chromatography tandem mass spectrometry (LC-MS/MS). The impacts of aeration and sunlight exposure were investigated. During the experiment, no elimination was observed for carbamazepine, triclosan, and ciprofloxacin while elimination was found for tetracycline, doxycycline, clindamycin, erythromycin, and clarithromycin. Using an availability-adjusted kinetic model, the 50% dissipation time was 37 to >77d for tetracycline, 53 to >77d for doxycycline, 1.0-1.6d for clindamycin, 1.1-1.9d for clarithromycin, and 7.0-17d for erythromycin. Those compounds were found more persistent under anaerobic conditions than aerobic condition with a longer 50% dissipation time by a factor of 1.5-2. However, minor impact was observed from sunlight irradiation.

Pharmaceutical compounds in the wastewater process stream in Northwest Ohio.

In order to add to the current state of knowledge regarding occurrence and fate of Pharmaceutical and Personal Care Products (PPCP's) in the environment, influent, effluent and biosolids from three wastewater treatment facilities in Northwest Ohio, USA, and a stream containing effluent discharge from a rural treatment facility were analyzed. The three WWTP facilities vary in size and in community served, but are all Class B facilities. One facility was sampled multiple times in order to assess temporal variability. Twenty compounds including several classes of antibiotics, acidic pharmaceuticals, and prescribed medications were analyzed using ultrasonication extraction, SPE cleanup and liquid chromatography-electrospray ionization tandem mass spectrometry. The highest number of compounds and the greatest concentrations were found in the influent from the largest and most industrial WWTP facility. Short-term temporal variability was minimal at this facility. Many compounds, such as clarithromycin, salicylic acid and gemfibrizol were found at concentrations more than one order of magnitude higher than found in the effluent samples. Effluent waters contained elevated levels of carbamazepine, clindamycin and sulfamethoxazole. Differences in composition and concentration of effluent waters between facilities existed. Biosolid samples from two different facilities were very similar in PPCP composition, although concentrations varied. Ciprofloxacin was found in biosolids at concentrations (up to 46 mug/kg dry mass) lower than values reported elsewhere. Diclofenac survived the WWTP process and was found to persist in stream water incorporating effluent discharge. The low variability within one plant, as compared to the variability found among different wastewater treatment plants locally and in the literature is likely due to differences in population, PPCP usage, plant operations and/or local environment. These data are presented here for comparison with this emerging set of environmental compounds of concern.

Assessing potential removal of low-head dams in urban settings: an example from the Ottawa River, NW Ohio.

This is a study of the scientific component of an effort to restore an urban river by removing a low-head dam. The Secor Dam is owned by a local government entity near Toledo, Ohio. The proposed removal of the last structure impeding flow on the Ottawa River has broad appeal, but the owner is concerned about liability issues, particularly potential changes to the flood regime, the presence of contaminated sediments behind the dam, and possible downstream transport of reservoir sediments. Assessing sediment contamination involved sediment sampling and analysis of trace metals and organic contaminants. Forecasting sediment transport involved field methods to determine the volume and textural properties of reservoir and upstream sediment and calculations to determine the fate of reservoir sediments. Forecasting changes in the flood regime involved HEC-RAS hydrological models to determine before and after dam removal flood scenarios using LiDAR data imported into an ArcGIS database. The resulting assessment found potential sediment contamination to be minor, and modeling showed that the removal of the dam would have minimal impacts on sediment transport and flood hazards. Based on the assessment, the removal of the dam has been approved by its owners.

PCB contamination in surface sediments in the coastal waters of Costa Rica

This paper describes the initial investigation of PCB concentrations in four geographical regions (three on the Pacific and one in the Caribbean) of coastal Costa Rica: Bahia Culebra, Golfo Dulce, Golfo de Nicoya, and Limón. Overall total concentrations of PCB were low in all areas except around the port of Golfito (Golfo Dulce). Overall average concentration is 2.80 ng/g dw, with a standard deviation of 2.75. The low concentration could be due to lack of contamination or the subsequent degradation in the warm climate, or the low sorptive capacity of the sediment. Further investigation is ongoing

Este articulo describe una investigación sobre las concentraciones de bifenilos policlorados (PCB) en cuatro regiones geográficas (tres en el Pacífico y una en el Caribe) costeras de Costa Rica.: Bahía Culebra, Golfo Dulce, Golfo de Nicoya, y Limón. Las concentraciones totales de PCB fueron bajas en todas las regiones excepto en el puerto de Golfito (Golfo Dulce). Las concentraciones promedio fueron de 2.80 ng /g dw, con una desviación estándar de 2.75. Las bajas concentraciones pueden estar asociadas a: la ausencia de contaminación por PCB, la degradación posterior en éste clima cálido, o la poca capacidad de absorción de los sedimentos

PCB concentrations in sediments from the Gulf of Nicoya estuary, Pacific coast of Costa Rica

Thirty-one sediment samples collected from 1996-2003 from the Gulf of Nicoya estuary on the north- western coast of Costa Rica, have been obtained for PCB analyses. This is part of the first study to evaluate the PCB contamination in coastal Costa Rica.Overall, the concentrations are low, especially when compared to sediments from more temperate climates and/or sediments from more heavily industrialized areas. Values average less than 3 ng/g dw sediment, however, a few samples contained up to 7 ng/g dw sediment. Sediments with the highest concentrations were located in the Punta Morales area, where muds were sampled from among mangrove roots. The Puntarenas samples had surprisingly low PCB concentrations, likely due to their sandy lithology. The congener distribution within the majority of the samples showed signs of either recent sources or lack of degradation. However, a few sites, specifically some of the inter-gulf islands and more remote samples had congener distributions indicative of airborne contaminants and/or degradation. Considering the presence of air-borne PCBs in the Gulf of Papagayo to the north, the lack of airborne PCBs and more varied congener distribution in the Gulf of Nicoya estuary was surprising

Se analizó los bifenilos policlorados (PCB) en 31 muestras de sedimentos colectadas entre 1996 -2003 en el estuario del Golfo de Nicoya, costa noroeste de Costa Rica. Esto es parte de un primer estudio para evaluar la contaminación por PCB en aguas costeras de Costa Rica. En general, las concentraciones fueron bajas especialmente cuando se les compara con sedimentos de climas templados y / o sedimentos de areas altamente industrializadas. Los valores promedio son inferiores a 3 ng / dw (peso seco) de sedimento. Sin embargo, unas pocas muestras contienen hasta 7 ng/ g dw de sedimento. Los sedimentos con las concentraciones más altas están localizados en el area de Punta Morales, en cienos de entre raíces de mangle. Las concentraciones de PCB en Puntarenas fueron sorprendentemente bajas, posiblemente por el tipo arenoso del sustrato. La distribución de congéneres dentro de la mayoría de las muestras muestran señal de una reciente contaminación o carencia de degradación . Sin embargo, en unos pocos sitios, específicamente en las islas internas del Golfo y otras areas más remotas tienen distribuciones de congéneres que indican contaminación por vía aerea y /o degradación. Cuando se considera la presencia de PCB transportados por via aerea en el Golfo de Papagayo al Norte, es sorprendente la ausencia en el Golfo de Nicoya de estos PCB y una distribución más variada de congéneres

PCB contamination in marine sediments from Golfo Dulce, Pacific coast of Costa Rica

Twenty-nine marine sediment samples collected from 1996 through 2002 from the Golfo Dulce embayment of Costa Rica were analyzed for PCB concentrations. The Esquinas River and Rincon Bay in the northern and western part of the gulf had relatively low overall concentrations of PCBs, with no samples having greater than 2.1 µg/g dw sediment. The Port of Golfito had the highest overall concentrations, ranging up to 15.7 µg/g dw sediment. These samples were also dominated by higher chlorinated congeners. Samples from the deeper (>100m) waters in the northern part of the gulf, as well as within the sediment plume from the Rio Coto Colorado had intermediate values. Within the Rio Coto Colorado sediment plume the concentrations did decrease with increasing depth and the congeners showed a shift towards less chlorinated congeners with depth. However, the deep northern basin had some of the highest PCB concentrations and the shift towards less chlorinated congeners was not apparent or significant. Whether the anoxic conditions that exist in the deep waters are capable of initiating dechlorination is still unknown. Overall, the data from Golfo Dulce show moderate PCB contamination, despite the pristine nature of the gulf and surrounding lands

Un total de 29 muestras de sedimentos recolectadas de 1996 a 2002 en el Golfo Dulce, Costa Rica fueron analizadas determinar las concentraciones de bifenilos policlorinados (PCBs). La Bahía de Rincón y el Río Esquinas en la parte noroeste del Golfo tienen concentraciones relativamente bajas de PCBs, con ninguna muestras superando los 2.1 ug/ dw (peso seco) de sedimento. El puerto de Golfito tuvo las mayores concentraciones hasta un máximo de 15.7 ug/g dw de sedimento. Estas muestras también estuvieron dominadas por los congéneres más clorinados. Las muestras de los sedimentos profundos (>100 m ) de las aguas de la parte norte del Golfo, así como las de la estela del Río Coto Colorado, tienen concentraciones intermedias. Dentro de la estela de sedimentos del Río Colorado las concentraciones aumentaron con la profundidad y los congéneres variaron con la profundidad hacia los menos clorinados. Sin embargo, la región profunda tuvo una de las más altas concentraciones de PCBs, pero la tendencia hacia los menos clorinados no fue aparente o significativa. No se conoce si las condiciones anóxicas en las aguas profundas son capaces de iniciar la declorización. En general, las muestras analizadas muestran concentraciones moderadas de PCBs, no obstante las condiciones pristinas del Golfo y su cuenca

PCB concentrations in sediments from the Gulf of Nicoya estuary, Pacific coast of Costa Rica.

Thirty-one sediment samples collected from 1996-2003 from the Gulf of Nicoya estuary on the northwestern coast of Costa Rica, have been obtained for PCB analyses. This is part of the first study to evaluate the PCB contamination in coastal Costa Rica. Overall, the concentrations are low, especially when compared to sediments from more temperate climates and/or sediments from more heavily industrialized areas. Values average less than 3 ng/g dw sediment, however, a few samples contained up to 7 ng/g dw sediment. Sediments with the highest concentrations were located in the Punta Morales area, where muds were sampled from among mangrove roots. The Puntarenas samples had surprisingly low PCB concentrations, likely due to their sandy lithology. The congener distribution within the majority of the samples showed signs of either recent sources or lack of degradation. However, a few sites, specifically some of the inter-gulf islands and more remote samples had congener distributions indicative of airborne contaminants and/or degradation. Considering the presence of airborne PCBs in the Gulf of Papagayo to the north, the lack of airborne PCBs and more varied congener distribution in the Gulf of Nicoya estuary was surprising.

PCB contamination in marine sediments from Golfo Dulce, Pacific coast of Costa Rica.

Twenty-nine marine sediment samples collected from 1996 through 2002 from the Golfo Dulce embayment of Costa Rica were analyzed for PCB concentrations. The Esquinas River and Rincon Bay in the northern and western part of the gulf had relatively low overall concentrations of PCBs, with no samples having greater than 2.1 microg/g dw sediment. The Port of Golfito had the highest overall concentrations, ranging up to 15.7 microg/g dw sediment. These samples were also dominated by higher chlorinated congeners. Samples from the deeper (> 100 m) waters in the northern part of the gulf, as well as within the sediment plume from the Rio Coto Colorado had intermediate values. Within the Rio Coto Colorado sediment plume the concentrations did decrease with increasing depth and the congeners showed a shift towards less chlorinated congeners with depth. However, the deep northern basin had some of the highest PCB concentrations and the shift towards less chlorinated congeners was not apparent or significant. Whether the anoxic conditions that exist in the deep waters are capable of initiating dechlorination is still unknown. Overall, the data from Golfo Dulce show moderate PCB contamination, despite the pristine nature of the gulf and surrounding lands.

PCB contamination in surface sediments in the coastal waters of Costa Rica.

This paper describes the initial investigation of PCB concentrations in four geographical regions (three on the Pacific and one in the Caribbean) of coastal Costa Rica: Bahia Culebra, Golfo Dulce, Golfo de Nicoya, and Limón. Overall total concentrations of PCB were low in all areas except around the port of Golfito (Golfo Dulce). Overall average concentration is 2.80 ng/g dw, with a standard deviation of 2.75. The low concentration could be due to lack of contamination or the subsequent degradation in the warm climate, or the low sorptive capacity of the sediment. Further investigation is ongoing.