Seasonal variations of several pharmaceutical residues in surface water and sewage treatment plants of Han River, Korea

We collected influent and effluent samples from four sewage treatment plants (STPs) as well as surface water samples in Han River of Seoul, Korea, in three sampling events representing different flow conditions, i.e., April, June, and August, 2005, and analyzed for eleven pharmaceuticals including acetaminophen, caffeine, carbamazepine, cimetidine, diltiazem, trimethoprim, and five sulfonamide antibiotics, using LC-MS-ESI. Pharmaceuticals of high annual production amount were detected in higher level in STP influents. Levels of pharmaceutical residues in the influents were the highest for acetaminophen (average 27,089 ng/L), followed by caffeine (23,664 ng/L), cimetidine (8045 ng/L), and sulfamethoxazole (523 ng/L). Levels of acetaminophen and caffeine in STP effluents were very low compared to the influent concentrations. However cimetidine was detected in relatively high levels even in STP effluent samples. In effluent samples, cimetidine showed the highest level (5380 ng/L), followed by caffeine (278 ng/L), sulfamethoxazole (193 ng/L), and carbamazepine (111 ng/L). The concentration of cimetidine was also the highest in surface water samples (average 281 ng/L), which is the highest level reported from surface water worldwide to our knowledge. Caffeine (268.7 ng/L), acetaminophen (34.8 ng/L), and sulfamethoxazole (26.9 ng/L) were also detected in relatively high levels. Levels of pharmaceuticals detected in surface water samples upstream STPs were generally very low compared to the downstream samples, suggesting that the STPs potentially be a major source of the test pharmaceuticals into Han River. The hazard quotients (HQs) were calculated for the test pharmaceuticals based on their occurrences in surface water, and no pharmaceutical resulted in HQ greater than one, suggesting that their potential environmental impact may be low.     

Occurrence and removal of pharmaceuticals and hormones through drinking water treatment

The occurrence of fifty-five pharmaceuticals, hormones and metabolites in raw waters used for drinking water production and their removal through a drinking water treatment were studied. Thirty-five out of fifty-five drugs were detected in the raw water at the facility intake with concentrations up to 1200 ng/L. The behavior of the compounds was studied at each step: prechlorination, coagulation, sand filtration, ozonation, granular activated carbon filtration and post-chlorination; showing that the complete treatment accounted for the complete removal of all the compounds detected in raw waters except for five of them. Phenytoin, atenolol and hydrochlorothiazide were the three pharmaceuticals most frequently found in finished waters at concentrations about 10 ng/L. Sotalol and carbamazepine epoxide were found in less than a half of the samples at lower concentrations, above 2 ng/L. However despite their persistence, the removals of these five pharmaceuticals were higher than 95%.     

The occurrence of pharmaceuticals, personal care products, endocrine disruptors and illicit drugs in surface water in South Wales, UK

The presence and fate of 56 pharmaceuticals, personal care products, endocrine disruptors and illicit drugs (PPCPs) were investigated in the South Wales region of the UK. Two contrasting rivers: River Taff and River Ely were chosen for this investigation and were monitored for a period of 10 months. The impact of the factors affecting the levels of concentration of PPCPs and illicit drugs in surface water such as surrounding area, proximity to wastewater effluent and weather conditions, mainly rainfall was also investigated. Most PPCPs were frequently found in river water at concentrations reaching single microgL(-1) and their levels depended mainly on the extent of water dilution resulting from rainfall. Discharge of treated wastewater effluent into the river course was found to be the main cause of water contamination with PPCPs. The most frequently detected PPCPs represent the group of pharmaceuticals dispensed at the highest levels in the Welsh community. These were antibacterial drugs (trimethoprim, erythromycin-H(2)O and amoxicillin), anti-inflammatories/analgesics (paracetamol, tramadol, codeine, naproxen, ibuprofen and diclofenac) and antiepileptic drugs (carbamazepine and gabapentin). Only four PPCPs out of 56 (simvastatin, pravastatin, digoxin and digoxigenin) were not quantified over the course of the study. Several PPCPs were found to be both ubiquitous and persistent in the aqueous environment (e.g. erythromycin-H(2)O, codeine, carbamazepine, gabapentin and valsartan). The calculated average daily loads of PPCPs indicated that in total almost 6 kg of studied PPCPs are discharged daily into the studied rivers. The illicit drugs studied were found in rivers at low levels of ng L(-1). Average daily loads of amphetamine, cocaine and its main metabolite benzoylecgonine were as follows: 8, 1.2 and 39 gday(-1), respectively. Their frequent occurrence in surface water is primarily associated with their high illegal usage and is strongly associated with the discharge of insufficiently treated wastewater effluent.     

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.     

Impacts of emerging organic contaminants on freshwater resources: review of recent occurrences, sources, fate and effects

Rapid urbanization and frequent disposal of wastewater to surface water cause widespread contamination of freshwater supplies with emerging contaminants, such as pharmaceuticals, insecticides, surfactants, endocrine disruptors, including hormones. Although these organic contaminants may be present at trace levels, their adverse effects on aquatic life, animals and even humans are a growing concern. Numerous studies have been published on the occurrence and fate of emerging organic contaminants in different parts of the world, spanning a wide range of sources and aquatic environments including freshwater catchments, effluent wastewater streams, lakes, rivers, reservoirs, estuaries and marine waters. This paper reviews recent studies on the occurrence and fate of frequently detected pharmaceuticals and hormones and identifies areas that merit further research.     

Historical contamination of Yukon Lake sediments by PCBs and organochlorine pesticides: influence of local sources and watershed characteristics

PCBs and other persistent organochlorine (OC) pesticides were analyzed in sediment cores collected from six lakes in Yukon Territory and one in northern British Columbia, Canada, with the objective of establishing sources and historical trends of these contaminants. DDT was found to be the most prominent OC in the sediment profiles of most of the lakes. Maximum sigmaDDT levels (3.47-2680 ng g(-1) dw) were observed in sediment slices dated to the 1950s from lakes near populated areas. In contrast, in more remote lakes (Hanson, Kusawa and Lindeman), the maximum sigmaDDT concentrations were observed in the sediments dated to the 1970s. Highest sigmaPCB and sigmaDDT concentrations were measured in sediments from Watson Lake, near a suspected PCB waste disposal site and in a region where DDT was heavily applied in the 1950s and 1960s. Elevated sigmaPCB concentrations [16.1-93.6 ng g(-1) dry weight (dw)] were also observed in sediments from lakes situated near populated areas, relative to Kusawa and Lindeman (11.1 and 12.7 ng g(-1) dw, respectively). Recent sigmaPCB fluxes ranged from 621 ng m(-2) y(-1) in Kusawa Lake to 16400 ng m(-2) y(-1) in Little Atlin Lake. The extremely high sedimentation rate (2050 g m(-2) y(-1)) in glacial fed Lindeman Lake gave rise to elevated fluxes of sigmaPCB (2410 ng m(-2) y(-1)) and other OCs, despite much lower concentrations in the sediment. Levels of hexachlorocyclohexanes (sigmaHCH), chlordane-related compounds (sigmaCHL), and chlorobenzenes (sigmaCBz) were in the low ng g(-1) (dw) range in all lake sediments, similar to concentrations previously reported for Arctic lakes in Canada, indicating that their major source was long range atmospheric transport. Contamination of the lakes with PCBs and DDT near populated areas of the Yukon Territory appears to be a result of regional activities rather than long range transport and deposition. The results also point to glacial runoff as a significant source of OCs to small, high elevation lakes (Lindeman), but not to larger lakes within the Yukon River drainage basin that are also affected by glacial sources (Kusawa, Laberge).     

Mercury in the Mackenzie River delta and estuary: Concentrations and fluxes during open-water conditions

Estimates of mercury (Hg) loadings to the Arctic Ocean from circumpolar rivers have not considered biogeochemical changes that occur when river water is temporarily stored in large deltas (delta effect). There are also few data describing Hg changes across the freshwater-saltwater transition zone (FSTZ) of these rivers. We assessed temporal changes in unfiltered total mercury (THg) and methylmercury (MeHg) concentrations during open-water 2004 in the Mackenzie River upstream of the Mackenzie River delta, and in 6 floodplain lakes across an elevation gradient. These data were used to calculate Hg fluxes from the Mackenzie River and to evaluate a delta effect on Hg using an estimate of delta river water storage and a mixing analysis. Mean THg concentrations were highest in river water (9.17 ± 5.51 ng/L) and decreased up the lake elevation gradient. Mean MeHg concentrations were highest in lakes periodically connected to the river (0.213 ± 0.122 ng/L) and MeHg concentrations in elevated lakes showed a mid-summer peak. Results from the mixing analysis showed that the delta effect may be large enough to affect Hg loadings to the Arctic Ocean. THg concentrations exiting the delta (10.2 ng/L) were 16% lower than those entering (12.1 ng/L), whereas MeHg showed little change. We calculated 2.5-month (open-water) THg and MeHg fluxes from the Mackenzie River of 1208 and 8.4 kg. These fluxes are similar in magnitude to previous annual estimates in the arctic literature suggesting that previously published annual Hg fluxes from the Mackenzie River may be large underestimates. We also assessed changes in Mackenzie River water THg and MeHg concentrations as it crossed the FSTZ during an open-water cruise. THg decreased non-conservatively across the estuary from 3.8-0.6 ng/L, possibly due to mixing and particle settling. MeHg concentrations were variable and near detection. Our results show that the Mackenzie River estuary is a dynamic environment and may have important controls on Hg delivered to the Arctic Ocean.     

Sources of pharmaceutical pollution in the New York City Watershed

An investigation was carried out in the New York City Watershed for the presence of selected pharmaceuticals. In four seasonal sampling events between August 2003 and May 2004, surface water was collected from eight reservoir keypoints and effluent was collected from four wastewater treatment plants. We evaluated the following twelve compounds: amoxicillin, atenolol, caffeine, carbamazepine, cephalexin, estrone, 17alpha-ethinylestradiol, 17beta-estradiol, ibuprofen, sulfamethoxazole, trimethoprim, and valproic acid. In the treated effluents, carbamazepine was detected most frequently (100%; concentration range: 22-551 ng/L), followed by atenolol (94%; ND - 14,200 ng/L), trimethoprim (83%; ND - 37,000 ng/L), ibuprofen (61%; ND - 14,600 ng/L), and caffeine (49%; ND - 37,200 ng/L), while estrone was detected once (56 ng/L). In the reservoir keypoint samples, only ibuprofen (2.5%; ND - 932 ng/L) and caffeine (2.9%; ND - 177 ng/L) were detected. The other analytes were not detected in any sample. It is expected that investigation of other wastewater treatment plants in the New York City Watershed would show that their effluents are also a potential source of pharmaceuticals, but that these pharmaceuticals are unlikely to be detected in the Watershed's surface waters.     

Occurrence of steroid estrogens, endocrine-disrupting phenols, and acid pharmaceutical residues in urban riverine water of the Pearl River Delta, South China

A scoping study was conducted to investigate the residues of nineteen pharmaceuticals and personal care products (PPCPs), including 4 natural and 3 synthetic steroid estrogens, 7 endocrine-disrupting phenols, and 5 acid pharmaceuticals in three urban streams and the Major Pearl River at Guangzhou, a megapolis in the Pearl River Delta, South China. Estrone was detected in >60% water samples with a maximum concentration of 65 ng L(-1). Endocrine-disrupting phenols (nonylphenol, bisphenol A, triclosan, 2-phenylphenol, methyparaben, and propylparaben) were found to be widely present at rather high concentrations in the urban riverine water of Guangzhou. Salicylic acid, clofibric acid and ibuprofen were detected in most water samples with maximum concentrations of 2098, 248 and 1417 ng L(-1) respectively, whereas naproxen was less frequently detected and also at lower concentration. Both the detection frequencies and median concentrations of the PPCPs appeared higher during the low-flow season than during the high-flow season. The seasonal difference in PPCPs occurrence was probably attributed to the dilution effect caused by the rainfall. PPCPs in the urban riverine water of Guangzhou originated mainly from random discharge and/or leakage of municipal wastewater. PPCPs contamination in the Major Pearl River may be of a potential environmental issue, especially during the low-flow season.     

Pharmaceutical chemicals and endocrine disrupters in municipal wastewater in Tokyo and their removal during activated sludge treatment

We measured six acidic analgesics or anti-inflammatories (aspirin, ibuprofen, naproxen, ketoprofen, fenoprofen, mefenamic acid), two phenolic antiseptics (thymol, triclosan), four amide pharmaceuticals (propyphenazone, crotamiton, carbamazepine, diethyltoluamide), three phenolic endocrine disrupting chemicals (nonylphenol, octylphenol, bisphenol A), and three natural estrogens (17beta-estradiol, estrone, estriol) in 24-h composite samples of influents and secondary effluents collected seasonally from five municipal sewage treatment plants in Tokyo. Aspirin was most abundant in the influent, with an average concentration of 7300 ng/L (n = 16), followed by crotamiton (921 ng/L), ibuprofen (669 ng/L), triclosan (511 ng/L), and diethyltoluamide (503 ng/L). These concentrations were 1 order of magnitude lower than those reported in the USA and Europe. This can be ascribed to lower consumption of the pharmaceuticals in Japan. Aspirin, ibuprofen, and thymol were removed efficiently during primary + secondary treatment (> 90% efficiency). On the other hand, amide-type pharmaceuticals, ketoprofen, and naproxen showed poor removal (< 50% efficiency), which is probably due to their lower hydrophobicity (logKow < 3). Because of the persistence of crotamiton during secondary treatment, crotamiton was most abundant among the target pharmaceuticals in the effluent. This is the first paper to report ubiquitous occurrence of crotamiton, a scabicide, in sewage. Because crotamiton is used worldwide and it is persistent during secondary treatment, it is a promising molecular marker of sewage and secondary effluent.     

Perfluorinated compounds in surface waters and WWTPs in Shenyang, China: mass flows and source analysis

Concentrations of 10 perfluorinated chemicals (PFCs) were investigated in the Hun River (HR), four canals, ten lakes, and influents and effluents from four main municipal wastewater treatment plants (WWTPs) in Shenyang, China. Mass flows of four main PFCs were calculated to elucidate the contribution from different sections of the HR. Overall, perfluorooctanoic acid (PFOA) and perfluorohexanoic acid (PFHxA) were the major PFCs in the HR, with ranges of 2.68-9.13 ng/L, and 2.12-11.3 ng/L, respectively, while perfluorooctane sulfonate (PFOS) was detected at lower levels, ranging from 0.40 to 3.32 ng/L. The PFC concentrations in the HR increased after the river passes through two cities (Shenyang and Fushun), indicating cities are an important contributor for PFCs. Mass flow analysis in the HR revealed that PFC mass flows from Fushun are 1.65-5.50 kg/year for C6-C8 perfluorinated acids (PFCAs) and 1.29 kg/year for PFOS, while Shenyang contributed 2.83-5.18 kg C6-C8 PFCAs/year, and 3.65 kg PFOS/year. The concentrations of PFCs in four urban canals were higher than those in the HR, with the maximum total PFCs of 240 ng/L. PFOA and PFOS showed different trends along these canals, suggesting different sources for the two PFCs. Total PFCs in ten lakes from Shenyang were at low levels, with the greatest concentration (56.2 ng/L) detected in a heavily industrialized area. The PFC levels in WWTP effluents were higher than those in surface waters with concentrations ranging from 18.4 to 41.1 ng/L for PFOA, and 1.69-3.85 ng/L for PFOS. Similar PFC profiles between effluents from WWTPs and urban surface waters were found. These results indicate that WWTPs are an important PFC source in surface water. Finally, we found that the composition profiles of PFCs in surface waters were similar to those in tap water, but not consistent with those in adult blood from Shenyang. The calculation on total daily intake of PFOS by adults from Shenyang showed that the contribution of drinking water to human exposure was minor.     

Trends of phosphorus,nitrogen and chlorophyll a concentrations in Finnish rivers and lakes in 1975-2000

During recent decades the amounts of nutrients discharged to Finnish surface waters have markedly decreased. This has been achieved by considerable investments in water protection, which were made mainly to improve municipal and industrial wastewater purification. We investigated whether these water protection measures have decreased phosphorus and nitrogen concentrations in Finnish rivers and lakes. In addition, possible trends in chlorophyll a concentrations in lakes were studied. The data consisted of a total of over 68000 monitoring results of 22 rivers and 173 lakes (or sub-basins of lakes) with different types of catchment areas. The study period covered the years 1975-2000 and the non-parametric Kendall Tau b and Seasonal Kendall tests were applied for detecting trends. Decreasing nutrient concentration trends were typical in many lakes and rivers earlier polluted by municipal and industrial wastewaters. Increasing nutrient concentration trends were common in smaller rivers and lakes receiving diffuse loading from agriculture. The results show that the investments directed towards wastewater purification have effectively improved the quality of Finnish inland waters. However, no clear effects of decreasing non-point loading were found. Thus, more effective measures should be directed towards decreasing non-point source loading.     

Trends of phosphorus, nitrogen and chlorophyll a concentrations in Finnish rivers and lakes in 1975–2000

During recent decades the amounts of nutrients discharged to Finnish surface waters have markedly decreased. This has been achieved by considerable investments in water protection, which were made mainly to improve municipal and industrial wastewater purification. We investigated whether these water protection measures have decreased phosphorus and nitrogen concentrations in Finnish rivers and lakes. In addition, possible trends in chlorophyll a concentrations in lakes were studied. The data consisted of a total of over 68 000 monitoring results of 22 rivers and 173 lakes (or sub-basins of lakes) with different types of catchment areas. The study period covered the years 1975–2000 and the non-parametric Kendall Tau b and Seasonal Kendall tests were applied for detecting trends. Decreasing nutrient concentration trends were typical in many lakes and rivers earlier polluted by municipal and industrial wastewaters. Increasing nutrient concentration trends were common in smaller rivers and lakes receiving diffuse loading from agriculture. The results show that the investments directed towards wastewater purification have effectively improved the quality of Finnish inland waters. However, no clear effects of decreasing non-point loading were found. Thus, more effective measures should be directed towards decreasing non-point source loading.     

Occurrence of endocrine disrupting compounds, pharmaceuticals, and personal care products in the Han River (Seoul, South Korea)

The occurrence of 31 selected endocrine disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs) in Korean surface waters was investigated. The area was selected since there is a lack of information in the Seoul area on the suspected contamination of rivers by micropollutants, although over 99% of drinking water is produced from surface waters in this area that has a population of approximately 15 million inhabitants. Samples were collected from upstream/downstream and effluent-dominated creeks along the Han River, Seoul (South Korea) and analyzed by liquid chromatography with tandem mass spectrometry (LC-MS/MS) with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI). Most target compounds were detected in both the Han River samples (63%) and the effluent-dominated creek samples (79%). Iopromide, atenolol, TCPP, TECP, musk ketone, naproxen, DEET, carbamazepine, caffeine, and benzophenone were frequently detected in both river and creek samples, although the mean concentrations in effluent-dominated creek samples (102 ng/L-3745 ng/L) were significantly higher than those in river samples (56 ng/L-1013 ng/L). However, the steroid hormones 17β-estradiol, 17α-ethynylestradiol, progesterone, and testosterone, were not detected (< 1 ng/L) in both the river and creek samples. Numerous target compounds (15) were found to be positively correlated (over 0.8) to the conventional water quality parameters (chemical oxygen demand, biochemical oxygen demand, dissolved organic carbon, and ultraviolet absorbance). Results of this study provide increasing evidence that certain EDCs and PPCPs commonly occur in the Han River as the result of wastewater outfalls.     

Occurrence and determination of a herbicide benthiocarb in rivers and agricultural drainages

The occurrence and determination of a herbicide, benthiocarb, 4-chlorobenzyl N,N-diethylthiolcarbamate (Saturn^®) in rivers and agricultural drainages was investigated. Benthiocarb residues were detected in water samples when it has been applied to rice paddies, after rice seedling transplantation, in concentrations of between 10.00 and 0.11 μg/l. These residues entered into rivers and agricultural drainages as a result of overflows from rice paddies. However, benthiocarb residues could not be found in water samples after the termination of its application to rice paddies, suggesting that the applied benthiocarb might be degraded by microbial and physico-chemical actions such as photochemical reactions occurring on the soil surface. Benthiocarb residue levels were higher in longer rivers than in agricultural drainage. The contribution of rainfall to the benthiocarb concentrations was shown. Benthiocarb in water was extracted with n-hexane and identified by a gas chromatography using a flame photometric detector (sulphur filter 394 nm) and a combined gas chromatography-mass spectrometry-computer system. The minimum detectable amount of benthiocarb in water sample by gas chromatography was 0.56 ng and about 100 ng of benthiocarb could be identified by a gas chromatography-mass spectrometry-computer system.     

Occurrence of pharmaceuticals in Taiwan's surface waters: Impact of waste streams from hospitals and pharmaceutical production facilities

We investigated the occurrence and distribution of pharmaceuticals (including antibiotics, estrogens, non-steroidal anti-inflammatory drugs (NSAIDs), beta-blockers, and lipid regulators) in three rivers and in the waste streams of six hospitals and four pharmaceutical production facilities in Taiwan. The most frequently detected pharmaceuticals were acetaminophen, erythromycin-H₂O, sulfamethoxazole, and gemfibrozil. NSAIDs were the next most-often detected compounds, with a detection frequency > 60%. The other analytes were not detected or were seen in only a few samples at trace concentrations. The present study demonstrates a significant discharge of human medications from hospital and drug production facilities into surface waters in the Taipei district. The high concentrations of pharmaceuticals found in the Sindian and Dahan rivers demonstrate the alarming degree to which they have been impacted by urban drainage (waste effluents from hospitals, households, and pharmaceutical production facilities). The ubiquitous occurrence at extremely high concentrations of acetaminophen and erythromycin-H₂O in both rivers (up to 15.7 and 75.5 µg/L) and in wastewater from hospitals and pharmaceutical production facilities (up to 417.5 and 7.84 µg/L) was unique. This finding, in combination with acetaminophen's status as the drug most often prescribed by Taiwan's dominant clinical institute, suggests the potential use of acetaminophen as a molecular indicator of contamination of Taiwan's aqueous environments with untreated urban drainage.     

Nationwide monitoring of selected antibiotics: Distribution and sources of sulfonamides, trimethoprim, and macrolides in Japanese rivers

We report the results of a nationwide survey of commonly used human and veterinary antibiotics (7 sulfonamides, trimethoprim, and 4 macrolides) in 37 Japanese rivers. Concentrations of the sum of the 12 target antibiotics ranged from undetectable to 626 ng/L, with a median of 7.3 ng/L for the 37 rivers. Antibiotics concentrations were higher in urban rivers than in rural rivers and were correlated with those of molecular markers of sewage (crotamiton and carbamazepine). Macrolides were dominant over sulfonamides in urban rivers. Sulfonamides, especially sulfamethazine (used in animals), were dominant in a few rivers in whose catchment animal husbandry is active. However, these signals of veterinary antibiotics were overwhelmed by those of human antibiotics in lower reaches of most rivers. The analysis of the antibiotics in all 88 samples showed that the target antibiotics in Japanese rivers are derived mainly from urban sewage, even though larger amounts of antibiotics are used in livestock. Most of the livestock waste-derived antibiotics are unlikely to be readily discharged to surface waters.     

Estimation of residual antibiotics in soil and underground water of areas affected by pharmaceutical wastewater in Lahore

Drinking water is most essential thing for life on earth. Due to environmental pollution day by day the quality and quantity of drinking water is lowering. Ground water tables are becoming contaminated due industrial pollution. Contamination level of antibiotics namely ofloxacin (OFL), ciprofloxacin (CIP), levofloxacin (LEV), oxytetracycline (OTC), doxycycline (DOX) were quantified in soil and underground water of surrounding areas of pharmaceutical industry in Lahore. HPLC with DAD detector, C-18 column and solid phase cartridges were used to analyze antibiotic residues. In groundwater DOX has highest mean level of contamination and OFL was determined as highest contaminating pollutant in soil. Highest detected value in groundwater of OFL was 0.50, CIP and LEV 0.20, DOX 0.80, OTC 0.40 ng/L. Ground water have residual level of CIP 0.01–0.20 ng/L, LEV 0.02–0.20 ng/L, OFL 0.01–0.50 ng/L, OTC 0.02–0.40 ng/L, and DOX 0.04–0.80 ng/L. Ground water was contaminated by these residues is very important as it is source of accumulation of antibiotics to human and animal body as well as to plants.     

Determination of phenolic endocrine disrupting chemicals and acidic pharmaceuticals in surface water of the Pearl Rivers in South China by gas chromatography-negative chemical ionization-mass spectrometry

An analytical method for phenolic endocrine disrupting chemicals and acidic pharmaceuticals in river water was developed using gas chromatography mass spectrometry (GC-MS) coupled with negative chemical ionization (NCI) technique, and used for the determination of these compounds in the Pearl Rivers (Liuxi, Zhujiang and Shijing Rivers). Derivatization using pentafluorobenzoyl chloride (PFBOCl) and pentafluorobenzyl bromide (PFBBr) before GC-MS analysis were applied and optimized for phenolic compounds and acidic compounds, respectively. The target compounds were analyzed for river waters from the upstream to downstream of the Pearl Rivers. Phenolic compounds 4-tert-octylphenol (4-t-OP), 4-nonylphenol (4-NP), bisphenol-A (BPA), estrone (E1), estradiol (E2) and triclosan (TCS) were detected at trace or low levels in the water samples from Liuxi River and Zhujiang River. Diethylstilbestrol (DES) was not detected in the Pearl Rivers. The highest concentrations of the phenolic compounds were found in Shijing River, and they were 3150 ng/L for 4-t-OP, 11,300 ng/L for 4-NP, 1040 ng/L for BPA, 79 ng/L for E1, 7.7 ng/L for E2 and 355 ng/L for TCS, respectively. Only a few acidic pharmaceuticals were detected at low concentrations in water from Liuxi River and Zhujiang River, but the highest concentrations for the acidic pharmaceuticals were also found in Shijing River. The highest concentrations detected for clofibric acid, ibuprofen, gemfibrozil, naproxen, mefenamic acid and diclofenac were 17 ng/L, 685 ng/L, 19.8 ng/L, 125 ng/L, 24.6 ng/l and 150 ng/L, respectively. The results suggest Liuxi and Zhujiang Rivers are only slightly contaminated and can be used as drinking water sources, but Shijing River is heavily polluted by the wastewater from nearby towns.     

Sulfur and strontium isotope geochemistry of tributary rivers of Lake Biwa: implications for human impact on the decadal change of lake water quality

To study the deterioration of the water quality in Lake Biwa, Japan, over the last 40 years, we measured the concentrations and isotopic ratios of sulfur and strontium of water in 41 inflowing rivers and one discharging river. The concentrations of SO4 and Sr of inflowing rivers at downstream sites were generally high in the southern urban area and in the eastern area, where a large agricultural plain is situated, but low in the northern and western areas, whose watersheds are mountainous and with low population density. SO4 and Sr concentrations are also lower at upstream sites, which are closer to mountainous areas. Thus, the inflowing river receives large amounts of SO4 and Sr as it flows across the plain, where human activity levels are high. The delta34S or 87Sr/86Sr values of most eastern rivers at downstream sites are lower than those of water in Lake Biwa, and values become more uniform as the proportion of the plain area in the watershed increases. River water in other areas has higher values of delta34S or 87Sr/86Sr than the lake water. This result indicates that the decadal decrease of delta34S and 87Sr/86Sr in the lake water has been caused mainly by the increased flux of SO4 and Sr from rivers in the eastern plain. We assume that in the plain, sulfur, nitrogen, and organic compounds induced by human activities generate sulfuric, nitric, and organic acids in the water, which accelerate the extraction of Sr from bedrocks, leading to the generation of Sr in the river water in the area.