Pharmaceuticals and personal care products (PPCPs) in surface and treated waters of Louisiana,USA and Ontario,Canada

A newly developed analytical method was used to measure concentrations of nine pharmaceuticals and personal care products (PPCPs) in samples from two surface water bodies, a sewage treatment plant effluent and various stages of a drinking water treatment plant in Louisiana, USA, and from one surface water body, a drinking water treatment plant and a pilot plant in Ontario, Canada. The analytical method provides for simultaneous extraction and quantification of the following broad range of PPCPs and endocrine-disrupting chemicals: naproxen; ibuprofen; estrone; 17beta-estradiol; bisphenol A; clorophene; triclosan; fluoxetine; and clofibric acid. Naproxen was detected in Louisiana sewage treatment plant effluent at 81-106 ng/l and Louisiana and Ontario surface waters at 22-107 ng/l. Triclosan was detected in Louisiana sewage treatment plant effluent at 10-21 ng/l. Of the three surface waters sampled, clofibric acid was detected in Detroit River water at 103 ng/l, but not in Mississippi River or Lake Pontchartrain waters. None of the other target analytes were detected above their method detection limits. Based on results at various stages of treatment, conventional drinking-water treatment processes (coagulation, flocculation and sedimentation) plus continuous addition of powdered activated carbon at a dosage of 2 mg/l did not remove naproxen from Mississippi River waters. However, chlorination, ozonation and dual media filtration processes reduced the concentration of naproxen below detection in Mississippi River and Detroit River waters and reduced clofibric acid in Detroit River waters. Results of this study demonstrate that existing water treatment technologies can effectively remove certain PPCPs. In addition, our study demonstrates the importance of obtaining data on removal mechanisms and byproducts associated with PPCPs and other endocrine-disrupting chemicals in drinking water and sewage treatment processes.     

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.     

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.     

Pharmaceuticals and personal care products (PPCPs) and endocrine disrupting chemicals (EDCs) in stormwater canals and Bayou St. John in New Orleans, Louisiana, USA

Samples were collected from two stormwater canals and a recreational urban waterway known as Bayou St. John in New Orleans, Louisiana, USA and analyzed for a range of pharmaceuticals and personal care products (PPCPs) and endocrine disrupting chemicals (EDCs). Concentrations of 7 PPCPs and EDCs were measured by a method that provides for simultaneous extraction and quantification of the following compounds: clofibric acid, naproxen, ibuprofen, fluoxetine, clorophene, triclosan, bisphenol A. The method also was used as an indicator of the occurrence of estrogenic compounds by targeting estrone and 17beta-estradiol. The two canals (Orleans and London) are used to drain a portion of the city's stormwater directly into the Mississippi River or Lake Pontchartrain. Bayou St. John is located between the two canals and supplied with water from Lake Pontchartrain. Results from the 6-month sampling period indicated the following concentration ranges for the two stormwater canals: naproxen (ND - 145 ng/l), ibuprofen (ND - 674 ng/l), triclosan (ND - 29 ng/l) and bisphenol A (1.9-158 ng/l). Concentrations of these target analytes increased with cumulative rainfall. For bayou waters, only naproxen (2.1-4.8 ng/l) and bisphenol A (0.9-44 ng/l) were detected. Estrone was detected but determined non-quantifiable for multiple sampling events at the 3 sites. None of the other target analytes (clofibric acid, fluoxetine, clorophene, and 17beta-estradiol) were detected above their method detection levels. Results of this study demonstrate the occurrence of PPCPs and EDCs in New Orleans stormwater canals and Bayou St. John. Results also demonstrate the use of this analytical technique as an indicator of non-point source sewage contamination in New Orleans stormwater canals.     

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 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.     

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.     

城市污水中的PPCPs及其去除特性

未被人体完全利用的药品和个人护理用品(PPCPs)会通过排泄或洗浴进入城市污水,水环境中的PPCPs正逐渐成为受人们关注的环境问题。为此介绍了有关城市污水中的PPCPs及其在污水处理厂中的去除特性和去除机理,并指出了在我国开展相关研究的必要性。     

Pharmaceutical and personal care products in tile drainage following land application of municipal biosolids

Land application of municipal biosolids (sewage) is a common farming practice in many parts of the world. There is potential for transport of pharmaceuticals and personal care products (PPCPs) from agricultural fields to adjacent surface waters via tile drainage systems. In this study, liquid municipal biosolids (LMB) (total solids=11,933 mg L(-1)), supplemented with selected PPCPs and the fluorescent dye tracer rhodamine WT (RWT), were applied to tile drained fields using two land application approaches. Objectives included evaluating the relative benefits of land application practices with respect to reducing PPCP loadings to tile drains, evaluating PPCP persistence in tile water, and determining whether rhodamine WT can be used to estimate PPCP mass loads in tile. The PPCPs examined included an antibacterial agent used in personal care products (triclosan), a metabolite of nicotine (cotinine), and a variety of drugs including two sulfonamide antimicrobials (sulfapyridine, sulfamethoxazole), a beta-blocker (atenolol), an anti-epileptic (carbamazepine), an antidepressant (fluoxetine), analgesic/anti-inflammatories (acetaminophen, naproxen, ibuprofen), and a lipid-regulator (gemfibrozil). Maximum observed PPCP concentrations in the spiked LMB were about 10(3) ng g(-1) dry weight. PPCPs were shown to move rapidly via soil macropores to tile drains within minutes of the land application. Maximum observed PPCP concentrations in tile effluent associated with the LMB application-induced tile flow event were approximately 10(1) to 10(3) ng L(-1). PPCP mass loads, for the application-induced tile-hydrograph event, were significantly (p<0.1) higher for surface spreading over non-tilled soil (incorporation tillage occurring 20 h post-application), relative to aerating soil immediately prior to surface spreading using an AerWay slurry deposition system. PPCP concentrations that were detected above the limit of quantitation (LOQ) in tile water during several precipitation-induced tile flow events that occurred post-application, included: triclosan (max. approximately 1.5 x 10(2) ng L(-1)), carbamazepine (max. approximately 7 x 10(1) ng L(-1)), atenolol (max approximately 4 x 10(1) ng L(-1)), and cotinine (max approximately 2 x 10(1) ng L(-1)). In spite of their presence in biosolids, the other PPCPs were not observed above LOQ concentrations during these events. PPCP concentrations were predicted from RWT concentrations over a 40 day study period. Tile mass loads as a percent of PPCP mass applied to soil ranged from 4.2%+/-SD of 9.2% to 7.1%+/-10.9% for the AerWay system and surface spreading plus incorporation treatments, respectively.     

珠三角城市群城镇用地扩展时空格局及其驱动因素分析

本文围绕着"珠三角城市群城镇用地如何扩展"及"扩展驱动力是什么"两个核心问题展开,基于2000-2015年珠三角城市群土地利用和社会经济数据,利用扩展强度和扩展差异指数分析了珠三角城市群城镇土地扩展的时空特征,选用空间杜宾模型和重心转移模型分析了珠三角城市群城镇用地扩展驱动力。结果表明:珠三角城市群整体扩展强度呈下降趋势,扩展差异显著,以广州市、深圳市为核心呈现蔓延式扩展;GDP、距核心城市的城镇距离是珠三角城市群城镇用地扩展的主要驱动因素;核心城市在促进其他城市的城镇用地增长方面发挥着重要作用。     

基于国家中心城市定位的广州核心职能研究

广州是经济总量全国第三大的城市,从城市职能看也体现了较强的自身特点,在全国城市体系中扮演着十分重要的角色。本文从历史视角对广州城市职能演变进行分析,运用统计分析和GIS技术,对广州的区域辐射范围进行研究,以2000-2005年全国城市统计资料为基准,探讨不同区域层面上的城市核心职能。在此基础上,结合国务院发布的《珠江三角洲改革发展规划纲要》提出把广州建设成为"国家中心城市"的定位,构建广州的核心职能体系。     

Occurrence and removal of antibiotics, hormones and several other pharmaceuticals in wastewater treatment plants of the largest industrial city of Korea

Occurrence and removal efficiencies of 20 pharmaceuticals and personal care products (PPCPs) including antibiotics, hormones, and several other miscellaneous pharmaceuticals (analgesics, antiepileptics, antilipidemics, antihypertensives, antiseptics, and stimulants) were investigated in five wastewater treatment plants (WWTPs) of Ulsan, the largest industrial city of Korea. The compounds were extracted from wastewater samples by solid-phase extraction (SPE) and analyzed by High-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). The results showed that acetaminophen, atenolol and lincomycin were the main individual pollutants usually found in concentrations over 10 μg/L in the sewage influent. In the WWTPs, the concentrations of analgesic acetaminophen, stimulant caffeine, hormones estriol and estradiol decreased by over 99%. On the contrary, the antibiotic sulfamethazine, the antihypertensive metoprolol, and the antiepileptic carbamazepine exhibited removal efficiencies below 30%. Particularly, removal of antibiotics was observed to vary between − 11.2 and 69%. In the primary treatment (physico-chemical processes), the removal of pharmaceuticals was insignificant (up to 28%) and removal of majority of the pharmaceuticals occurred during the secondary treatment (biological processes). The compounds lincomycin, carbamazepine, atenolol, metoprolol, and triclosan showed better removal in WWTPs employing modified activated sludge process with co-existence of anoxic-oxic condition. Further investigation into the design and operational aspects of the biological processes is warranted for the efficient removal of PPCPs, particularly antibiotics, to secure healthy water resource in the receiving downstream, thereby ensuring a sustainable water cycle management.     

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 μg 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.     

城市大型公共空间使用频率影响因素研究——花城广场与珠江公园使用后评估

花城广场与珠江公园同处于广州新城市中心区珠江新城内,相距约1km,都是绿化环境优美的城市大型公共空间。花城广场南端的海心沙岛是举办2010年第十六届亚运会开闭幕式的庆典广场,花城广场已是广州乃至中国家喻户晓的“城市客厅”。2001年10月至2002年3月,中国第四届园林博览会在珠江公园召开。这两处城市公共空间具有相似的区位、规模和绿化环境,但市民对两者的使用频率却差异较大。现对两地的使用情况进行现场调研和问卷调查,将收集到的数据采用频数分析、配对样本参数检验和单因素方差分析方法进行统计分析,发掘普通市民对两者评价满意度差异,进而探讨城市大型公共空间使用频率的影响因素。     

市政法规影响下的民国广州沿江商业空间特征 ——以长堤周边路段骑楼底空间为例

民国初期开始的市政法规颁行是近代广州城市演进历史上的重要事件,需评估其对城市空间转型造成的影响。以微小尺度的城市空间为观察窗,以民国时期广州市政法规的演进为切入点,研究自清末民初至1930 年代广州沿江商业街长堤的空间特征,对比其周边两段典型街道的骑楼底空间演变,探究近代市政法规引导城市空间转型与发展的过程。认为源自不同社会团体博弈与平衡的市政法规演变,直接作用于商业空间并重塑其形态,决定了近代广州的沿江街道面貌。     

明成化年间文溪改道对广州城市人居环境的影响

文溪在广州城的起源和发育阶段, 具有供水、排水、防洪、防御和交通的多重功 能,是广州城的立城之源。广州城常受季节 性洪涝灾害的威胁,隋唐采用以“蓄”为主的 排水策略,宋代则改为以“导”为主,在解决 水患的同时,营造了良好的人居环境。明代 广州城市扩张,致使水患加剧。为应对灾害, 地方官民迫使文溪改道,由此出现了水体萎 缩、积水成患等水环境效应。水系的改变带 动了城市人居环境的变迁,广州的发展呈现 出—?—城市街道“内聚外扩”,功能分区“内 缩西迁”,景观体系“内消北移”的结构性重 组,土地利用性质也随之发生改变。文溪改 道虽然在短时间内抑制了城市洪灾的发生, 但未能彻底解决水患,绵延清代数百年仍未 解决,广州城也因此失去了水城的人居景观 特色。结合GIS分析,研究表明,重视城市水 循环系统、厘清水的脉络再对水系进行改造是非常重要的,以期为当代城市防洪和人居环境建设提供经验。     

Demonstration of 20 pharmaceuticals and personal care products (PPCPs) as nitrosamine precursors during chloramine disinfection

The worldwide detection of pharmaceuticals and personal care products (PPCPs) in the aquatic environment and drinking water has been a cause for concern in recent years. The possibility for concurrent formation of nitrosamine DBPs (disinfection by-products) during chloramine disinfection has become another significant concern for delivered drinking water quality because of their potent carcinogenicity. This study demonstrates that a group of PPCPs containing amine groups can serve as nitrosamine precursors during chloramine disinfection. Molar yields higher than 1% are observed for eight pharmaceuticals, with ranitidine showing the strongest potential to form N-nitrosodimethylamine (NDMA). The molar conversion increases with the Cl₂:N mass ratio, suggesting that dichloramine is relevant to the formation of NDMA from these precursors. Although the trace level of PPCPs in the environment suggests that they may not account for the majority of nitrosamine precursors during the disinfection process, this study demonstrates a connection between the transformation of PPCPs and the formation of nitrosamines during chloramine disinfection. This both expands the pool of potential nitrosamine precursors, and provides a possible link between the presence of trace levels of certain PPCPs in drinking water sources and potential adverse health effects.     

珠江·广州城·湾区城市——由"广州港湾广场"规划与建筑设计国际邀请赛引发的思考

本文介绍了在“广州港湾广场的设计中，通过从历史、未来发展及空间构成关系三方面对珠江与广州城市的关系，在遵循城市设计原则的同时，注重塑造沿珠江的亲水建筑方案。     

Runoff of pharmaceuticals and personal care products following application of biosolids to an agricultural field

Municipal biosolids are a source of nutrients for crop production. Beneficial Management Practices (BMPs) can be used to minimize the risk of contamination of adjacent water resources with chemical or microbial agents that are of public or environmental health concern. In this field study, we applied biosolids slurry at a commercial rate using either subsurface injection or broadcast application followed by incorporation. Precipitation was simulated at 1, 3, 7, 22, 36 and 266 days post-application on 2 m² microplots to evaluate surface runoff of 9 model pharmaceuticals and personal care products (PPCPs), atenolol, carbamazepine, cotinine, gemfibrozil, naproxen, ibuprofen, acetaminophen, sulfamethoxazole and triclosan. In runoff from the injected plots, concentrations of the model PPCPs were generally below the limits of quantitation. In contrast, in the broadcast application treatment, the concentrations of atenolol, carbamazepine, cotinine, gemfibrozil, naproxen, sulfamethoxazole and triclosan on the day following application ranged from 70-1477 ng L^− 1 in runoff and generally declined thereafter with first order kinetics. The total mass of PPCPs mobilized in surface runoff per m² of the field ranged from 0.63 µg for atenolol to 21.1 µg for ibuprofen. For ibuprofen and acetaminophen, concentrations in runoff first decreased and then increased, suggesting that these drugs were initially chemically or physically sequestered in the biosolids slurry, and subsequently released in the soil. Carbamazepine and triclosan were detected at low concentrations in a runoff event 266 days after broadcast application. Overall, this study showed that injection of biosolids slurry below the soil surface could effectively eliminate surface runoff of PPCPs.