Occurrence and fate of synthetic musk compounds in water environment

Synthetic musk compounds (SMCs) occur widely in water environments. The aims of this paper were to investigate the occurrence and fate of SMCs in sewage treatment plants (STPs) and surface waters. Total SMC concentrations ranged from 3.69 to 7.33 μg/L (influent) and from 0.96 to 2.69 μg/L (effluent) in 10 STPs. The SMC concentrations varied with the input source and treatment volume of each STP. Biological treatment processes had a greater SMCs removal effect than chemical treatment, filtration and disinfection processes. The SMC concentrations in surface waters ranged from 0.15 to 16.72 μg/L and exhibited similar SMCs occurrence patterns generally. The fate of SMCs in water environments depends on their physical-chemical properties and their concentrations can be predicted from other SMC concentrations due to their similar fates.     

Prediction of corrosion-induced cover cracking in reinforced concrete structures

Usually, the time of repair/replacement of reinforced concrete structures due to corrosion is controlled by cracking of the concrete cover. Thus, it is important to be able to predict with sufficient accuracy the time from corrosion initiation to crack formation in the concrete cover. The paper presents a critical overview of existing empirical, analytical and numerical models for predicting the time to corrosion-induced cover cracking. A simple nonlinear finite element (FE) is then formulated and validated. The FE model is employed to investigate inaccuracies of analytical models arising due to simplified formulation of the nonlinear behaviour of concrete and inability to account for actual location of corroding reinforcing bars. Recommendations on the applicability of analytical models are provided. Finally, the FE model is used to estimate the amount of corrosion products penetrating into concrete pores and microcracks since this amount is an essential parameter for analytical and numerical models.     

锈蚀钢筋混凝土保护层锈胀开裂时间的预测模型

由钢筋锈蚀引起的混凝土保护层锈胀开裂是混凝土结构耐久性极限状态的重要标志,是决定结构使用寿命的重要因素。以钢筋均匀锈蚀为前提,考虑锈蚀产物的变形特性以及锈胀裂缝开展过程中锈蚀产物进入裂缝的实际情况,借助弹性力学和Faraday腐蚀定律,建立混凝土保护层锈胀开裂时刻的钢筋锈蚀率以及锈胀开裂时间计算公式。针对影响混凝土保护层锈胀开裂时间各主要因素的分析表明,增大钢筋的混凝土保护层厚度、减小钢筋直径、提高混凝土强度以及控制锈蚀产物的体积膨胀率都有利于混凝土结构耐久性的提高。与已有试验结果的对比分析可知,对于加速锈蚀和长期锈蚀情况,计算公式的预测结果均较为理想,可用于由钢筋均匀锈蚀引起的混凝土保护层锈胀开裂时间的预测分析。     

混凝土结构锈裂形态试验研究及数值模拟

混凝土结构服役后期会出现保护层剥落的情况,混凝土保护层剥落与内部锈胀裂缝的分布情况密切相关。通过对不同尺寸与配筋情况的混凝土试块进行内部锈胀裂缝开展与分布研究,采用改进通电加速锈蚀方法加速试块劣化,通过切片观测锈蚀后试块内部锈胀裂缝形态,研究箍筋、保护层厚度、钢筋间距对内部锈胀裂缝开展的影响。研究结果表明：箍筋显著改变了内部锈胀裂缝开展与分布情况;混凝土保护层厚度较小或钢筋间距较大时,钢筋锈胀裂缝表现为单根锈胀开裂形式,反之则表现为钢筋之间的水平贯通裂缝。基于黏聚力单元建立了有限元分析模型,将钢筋锈胀变形作为位移加载依据,对试块锈裂过程进行数值分析,模拟结果与试验结果吻合较好。     

混凝土结构锈胀裂缝中铁锈分布的试验研究

混凝土结构锈胀开裂是导致混凝土结构耐久性失效的主要原因.在锈胀开裂过程中,铁锈是否填充到锈胀开展的裂缝中,是影响锈裂模型预测结果准确与否的重要因素之一.对人工气候环境下加速劣化的混凝土试块进行切片研究,采用数码显微镜观察了混凝土锈胀开裂裂缝中铁锈分布的情况,由此分析随裂缝开展铁锈发展的过程.试验研究认为,对于外裂裂缝,在裂缝开展到保护层表面之前,铁锈对裂缝的填充可忽略不计;只有在裂缝贯通到保护层表面后,铁锈才会逐渐填入钢筋附近的裂缝之中,并能在较远位置的裂缝边缘观察到铁锈的吸附.而对于内裂裂缝,钢筋锈蚀到一定程度后,也会有少量的铁锈填入裂缝中,但填充过程要缓慢得多.铁锈发展的这一特性,对混凝土结构锈裂过程的分析和合理锈裂模型的建立具有非常重要的指导意义.     

Storm water runoff measurements of copper from a naturally patinated roof and from a parking space. Aspects on environmental fate and chemical speciation

Release of copper from a naturally aged copper roof on a shopping centre building in a suburban site of Stockholm has been measured during different rain events after its interaction with the internal drainage system and storm drains made of cast iron and concrete. Concentrations of copper removed by means of urban storm water from a nearby parking space have been determined for comparison. Predictions and measurements of the chemical speciation of released copper are discussed compared to the total concentration, and to threshold values for freshwater and drinking water.The results clearly illustrate that the major part of the released copper from the roof is readily retained already during transport through the internal drainage system of the building, a pathway that also changes the chemical speciation of released copper and its bioavailable fraction. Most copper, not retained by cast iron and concrete surfaces, was strongly complexed to organic matter. The median concentration of free cupric ions and weak copper complexes was less than, or within the range of reported no effect concentrations, NOECs, of copper in surface waters. The parking space contributed with significantly higher and time-dependent concentrations of total copper compared to measured concentrations of copper from the roof after the interaction with the drainage system. Most copper in the surface runoff water was strongly complexed with organic matter, hence reducing the bioavailable fraction significantly to concentrations within the NOEC range. Dilution with other sources of urban storm water will reduce the released concentration of copper even further.The results illustrate that already the internal drainage system and the storm drains made of cast iron and concrete act as efficient sinks for released copper which means that any installation of additional infiltration devices is redundant.     

Probabilistic service life of reinforced concrete structures with randomly distributed corrosion-induced cracks

This paper proposed a probabilistic service life prediction method for reinforced concrete (RC) structures with randomly distributed chloride corrosion-induced cracking. In the proposed method, spatial randomness of environmental, geometric and physical factors was considered that influence corrosion process and crack propagation of RC structures at the material level. Karhunen–Loéve (KL) expansion method was utilised for modelling the spatial random fields. Four limit state functions were proposed based on four deterioration events (corrosion initiation, surface crack initiation, modulus degradation and exceedance of repair limit). Then, time-dependent reliability analyses of an RC bridge slab were conducted using the proposed method. Finally, sensitivity analysis of the statistical parameters including mean, variance, correlation length as well as the truncation number for KL expansion method were conducted to determine the effects of those parameters to the service life.     

Occurrence and fate modeling of MTBE and BTEX compounds in a Swiss Lake used as drinking water supply

Emissions of fuel components from boating use on multiple-use lakes and reservoirs are of high concern with regard to the drinking water supply from such water bodies. We report results of a detailed study on the occurrence, sources and fate of aromatic hydrocarbons and methyl tert-butyl ether (MTBE) in a typical holomictic lake, Lake Zurich, that supplies drinking water for the largest Swiss city. Emphasis of the investigation was on the fuel oxygenate MTBE, which was found in concentrations up to 1.4 microg/L in the epilimnion and up to 0.05microg/L in the hypolimnion of the lake. The concentration difference was due to the stratification of the lake during the boating season with very limited water exchange across the thermocline. MTBE and BTEX nearly completely volatilized before vertical lake mixing occurred in winter. Spatial and temporal variations of MTBE concentrations in the lake were observed and successfully predicted using two complementary box models (MASAS Light and Aquasim). The drinking water supply from holomictic lakes is not at risk for the scenarios studied if water is extracted from well below the thermocline. Since emissions of unburned gasoline into such water bodies are caused predominantly by boating activities, restrictions of highly emitting two-stroke engines could substantially reduce the MTBE and BTEX load of the epilimnion during the boating season.     

Ecological risk assessment of zinc from stormwater runoff to an aquatic ecosystem

Zinc (Zn) risks from stormwater runoff to an aquatic ecosystem were studied. Monitoring data on waterborne, porewater, and sediment Zn concentrations collected at 20 stations throughout a stormwater collection/detention facility consisting of forested wetlands, a retention pond and first order stream were used to conduct the assessment. Bioavailability in the water column was estimated using biotic ligand models for invertebrates and fish while bioavailability in the sediment was assessed using acid volatile sulfide-simultaneously extracted metal (AVS-SEM). The screening level assessment indicated no significant risks were posed to benthic organisms from Zn concentrations in sediments and pore water. As would be expected for stormwater, Zn concentrations were temporally quite variable within a storm event, varying by factors of 2 to 4. Overall, probabilistic assessment indicated low (5-10% of species affected) to negligible risks in the system, especially at the discharge to the first order stream. Moderate to high risks (10-50% of species affected) were identified at sampling locations most upgradient in the collection system. The largest uncertainty with the assessment is associated with how best to estimate chronic exposure/risks from time-varying exposure concentrations. Further research on pulse exposure metal toxicity is clearly needed to assess stormwater impacts on the environment.     

Occurrence and fate of TMDD in wastewater treatment plants in Germany

The occurrence and fate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD) was investigated in four wastewater treatment plants (WWTPs) in Germany. The concentration of TMDD in influents and effluents in the WWTPs ranged from 134 ng/L to 5846 ng/L and from <LOQ to 3539 ng/L correspondingly. Loads determined in influents (10.1 g/d-1142 g/d) and effluents (<LOQ - 425 g/d) indicate that TMDD is partially removed from the wastewater. The elimination rates varied between 33% and 68%. Based on the load analysis, the TMDD effluent discharge of WWTPs investigated varied from 8.29 kg/a to 52.6 kg/a. Day and week profiles were recorded and indicated that TMDD is introduced into the sewage through household and indirect dischargers with high fluctuations. Seasonal variations in the TMDD loads were also analyzed in three of the studied WWTPs. One of the WWTPs demonstrated statistically higher TMDD loads during the warm period (164 g/d) than during the cold period (91.3 g/d), for the others WWTPs any differences could not be established. The input of TMDD during weekends and working days was also studied. The results did not show any significant trend of TMDD discharge into the WWTPs.     

Occurrence and fate of the antidiabetic drug metformin and its metabolite guanylurea in the environment and during drinking water treatment

Metformin, an antidiabetic drug with one of the highest consumption rates of all pharmaceuticals worldwide, is biologically degraded to guanylurea in wastewater treatment plants. Due to high metformin influent concentrations of up to 100 μg/L and its high but incomplete degradation both compounds are released in considerable amounts of up to several tens of μg/L into recipient rivers. This is the first systematic study on their environmental fate and the effectiveness of treatment techniques applied in waterworks to remove metformin and guanylurea from surface water influenced raw waters. The concentrations in surface waters depend strongly on the respective wastewater burden of rivers and creeks and are typically in the range of about 1 μg/L for metformin and several μg/L for guanylurea but can reach elevated average concentrations of more than 3 and 20 μg/L, respectively. Treatment techniques applied in waterworks were investigated by an extended monitoring program in three facilities and accompanied by laboratory-scale batch tests. Flocculation and activated carbon filtration proved to be ineffective for removal of metformin and guanylurea. During ozonation and chlorination experiments with waterworks-relevant ozone and chlorine doses they were partly transformed to yet unknown compounds. The effectiveness of the treatment steps under investigation can be ordered chlorination > ozonation > activated carbon filtration > flocculation. However, most effective for removal of both compounds at the three full-scale waterworks studied proved to be an underground passage (riverbank filtration or artificial groundwater recharge). A biological degradation is most likely as sorption can be neglected. This is based on laboratory batch tests conducted with three different soil materials according to OECD guideline 106. Since such treatment steps were implemented in all three drinking water treatment plants, even traces of metformin and its metabolite guanylurea could not be detected at the end of the treatment trains. Both can only be expected in finished drinking water if surface influenced raw water is used by direct abstraction without underground passage.     

Occurrence and fate of endocrine disrupters in Greek sewage treatment plants

The occurrence of five endocrine-disrupting compounds (EDCs), namely 4-n-nonylphenol (4-n-NP), nonylphenol monoethoxylate (NP1EO), nonylphenol diethoxylate (NP2EO), triclosan (TCS) and bisphenol A (BPA), was assessed in the raw, treated wastewater and sewage sludge of eight sewage treatment plants (STPs) in Greece. The analytes were extracted by solid-phase extraction (dissolved phase) or sonication (solid phase). Qualitative and quantitative analyses were performed by gas chromatography-mass spectrometry (GC-MS). The average concentrations in the raw and treated wastewater ranged from 0.23 (4-n-NP) to 5.76microgL(-1) (NP1EO) and from 0.15 (BPA) to 1.84microgL(-1) (NP2EO), respectively. A great part of the detected EDCs was sorbed on suspended solids. In sewage sludge, the average concentrations ranged between 0.17 (4-n-NP) and 12.3microgg(-1)dw (NP1EO). Analysis of daily mass flows in STP of Athens showed that, with the exception of 4-n-NP, all other EDCs were significantly removed (>85%) during wastewater treatment. Regarding the fate of these compounds, a significant part ranging from 45% (for TCS) to more than 70% (for NP1EO, NP2EO and BPA) was transformed by abiotic or biotic mechanisms, while the rest was accumulated in sewage sludge or disposed to the environment via the effluents. Calculation of risk quotients showed the existence of possible threat due to the presence of certain EDCs in treated wastewater and sludge.     

Occurrence and fate of emerging wastewater contaminants in Western Balkan Region

This paper reports on a comprehensive reconnaissance of over seventy individual wastewater contaminants in the region of Western Balkan (WB; Bosnia and Herzegovina, Croatia and Serbia), including some prominent classes of emerging contaminants such as pharmaceuticals and personal care products, surfactants and their degradation products, plasticizers, pesticides, insect repellents, and flame retardants. All determinations were carried out using a multiresidue analytical approach, based on the application of gas chromatographic and liquid chromatographic techniques coupled to mass spectrometric detection. The results confirmed a widespread occurrence of the emerging contaminants in municipal wastewaters of the region. The most prominent contaminant classes, determined in municipal wastewaters, were those derived from aromatic surfactants, including linear alkylbenzene sulphonates (LAS) and alkylphenol polyethoxylates (APEO), with the concentrations in raw wastewater reaching into the mg/l range. All other contaminants were present in much lower concentrations, rarely exceeding few microg/l. The most abundant individual compounds belonged to several classes of pharmaceuticals (antimicrobials, analgesics and antiinflammatories, beta-blockers and lipid regulators) and personal care products (fragrances). Due to the rather poor wastewater management practices in WB countries, with less than 5% of all wastewaters being biologically treated, most of the contaminants present in wastewaters reach ambient waters and may represent a significant environmental concern.     

Occurrence and fate of antibiotics in the Seine River in various hydrological conditions

Occurrence and fate of 17 antibiotics were investigated in the aqueous phase of river water under different hydrological conditions at 5 sampling locations in the Seine River inner estuary. The target analytes belonged to 4 groups: quinolones, sulfonamides, nitro-imidazoles and diaminopyrimidines. This six-month survey (from January to June 2006) showed that different compounds were occurring at individual concentrations reaching 544 ng L(-)(1) (sulfamethoxazole). All 17 compounds were detected at least once in the survey. Sulfamethoxazole was detected in every sample, and showed the highest concentrations. Norfloxacin and flumequine were found to be the most ubiquitous quinolones, with detection frequencies of 33 and 75% respectively at the most contaminated site (Poses). Investigations concerning the origins of this contamination were made by means of a longitudinal profile along the Seine River between Paris and Poses. It showed large inputs of norfloxacin, ofloxacin, trimethoprim and sulfamethoxazole from wastewater treatment plants, with an increase in norfloxacin and sulfamethoxazole concentrations of 84% and 70% respectively, both reaching 155 ng L(-)(1) in the river, downstream from a wastewater outlet. The detected compounds showed different dissipation patterns and behaviours under different hydrological conditions. Higher inputs of norfloxacin were found in low flow conditions, which were rapidly attenuated along the stream. In contrast, sulfamethoxazole inputs were increasing in high flow conditions, and dissipation of this compound was found to be slow. Similar behaviour was observed for the synergist trimethoprim. Flumequine was also frequently detected and its input increased during flood events.     

Performance of grass swales for improving water quality from highway runoff

The performance of grass swales for treating highway runoff was evaluated using an experimental design that allowed for influent and effluent flow and pollutant concentration measurements to be taken at specific intervals through each storm event. Two common swale design alternatives, pre-treatment grass filter strips and vegetated check dams, were compared during 45 storm events over 4.5 years. All swale alternatives significantly removed total suspended solids and all metals evaluated: lead, copper, zinc, and cadmium. The probability of instantaneous concentrations exceeding 30 mg/L TSS was decreased from 41–56% in the untreated runoff to 1–19% via swale treatment. Nutrient treatment was variable, with generally positive removal except for seasonal events with large pulses of release from the swales. Nitrite was the only consistently removed nutrient constituent. Chloride concentrations were higher in swale discharges in nearly every measurement, suggesting accumulation during the winter and release throughout the year. Sedimentation and filtration within the grass layer are the primary mechanisms of pollutant treatment; correspondingly, particles and particulate-bound pollutants show the greatest removal via swales. Inclusion of filter strips or check dams had minimal effects on water quality.     

水中微量锌的测定

为实现在水相直接光度测定,在总结相关工作经验的基础上,研究了在非离子型表面活性剂TritonX-100存在下,双硫腙与锌的显色反应,结果表明,在HAC,NaAc缓冲介质中,锌与双硫腙形成红色络合物,采用该方法测定水中锌含量操作简单快速,值得推广。     

Phosphodiesterase type V inhibitors: Occurrence and fate in wastewater and sewage sludge

The contamination of wastewater and sewage sludge has been examined for three phosphodiesterase type V inhibitors sildenafil, vardenafil and tadalafil, active agents of Viagra^®, Levitra^® and Cialis^®, respectively. Sensitive quantification methods based on solid-phase extraction (SPE) and pressurized liquid extraction (PLE) followed by high performance liquid chromatography - tandem mass spectrometry (HPLC-MS/MS) have been developed to analyse these compounds in wastewater and sewage sludge.Effluent water of nine sewage treatment plants (STPs) has been analysed to assess the impact of the phosphodiesterase type V inhibitors on the environment. One municipal STP (Tarragona, Spain) has been thoroughly studied over the year 2008 (i) with respect to the distribution of these compounds among influent and sewage sludge and (ii) the elimination efficiency.The developed methods allowed quantification at trace concentrations. Sildenafil was present in all investigated samples at the low ng/L and ng/g range, respectively. Tadalafil was not detected or below the limit of detection (LOQ) in effluent water taken in Spain but in sewage sludge (12 ng/g -  < LOQ). Vardenafil was present only in one sludge sample and between 5 ng/g and < LOQ in effluent water. The overall removal efficiency of the STP in Tarragona (Spain) is 68%, 69% and 80% for sildenafil, tadalafil and vardenafil, respectively. This study shows for the first time the determination of these compounds in wastewater and sewage sludge.     

Occurrence and fate of quinolone and fluoroquinolone antibiotics in a municipal sewage treatment plant

This study developed a method for analysis of nineteen quinolone and fluoroquinolone antibiotics (FQs) in sludge samples, and investigated the occurrence and fate of the FQs in a municipal sewage treatment plant (STP) with anaerobic, anoxic, and aerobic treatment processes. Eleven compounds, including pipemidic acid, fleroxacin, ofloxacin, norfloxacin, ciprofloxacin, enrofloxacin, lomefloxacin, sparfloxacin, gatifloxacin, moxifloxacin, and sarafloxacin (only in sludge), were detected in the STP. The predominance of ofloxacin and norfloxacin, followed by lomefloxacin, ciprofloxacin, gatifloxacin, and moxifloxacin, were found in wastewater, suspended solids, and sludge. The total concentrations of FQs were 2573 ± 241 ng/L, 1013 ± 218 ng/L, and 18.4 ± 0.9 mg/kg in raw sewage, secondary effluent, and sludge, respectively. Extremely low mass change percentages were observed for FQs in anaerobic, anoxic, and aerobic treatment units, suggesting biodegradation to be of minor importance in the removal of FQs in STPs. 50-87% of the initial FQs loadings (except for pipemidic acid (36%)) were ultimately found in the dewatered sludge. Mean removal efficiencies of FQs in the STP were 56-75%, except for new generation drugs such as moxifloxacin (40 ± 5%) and gatifloxacin (43 ± 13%). A significant positive correlation was found between removal efficiencies and K_d of FQs. The major factor in the removal of FQs in the STP was sorption to sludge, which was not governed by hydrophobic interactions. The long-term cycling and persistence of FQs in the STP has made activated sludge as a huge reservoir of FQ antibiotics.     

Monitoring of water quality from roof runoff: Interpretation using multivariate analysis

The quality of harvested rainwater used for toilet flushing in a private house in the south-west of France was assessed over a one-year period. Temperature, pH, conductivity, colour, turbidity, anions, cations, alkalinity, total hardness and total organic carbon were screened using standard analytical techniques. Total flora at 22 °C and 36 °C, total coliforms, Escherichia coli and enterococci were analysed. Overall, the collected rainwater had good physicochemical quality but did not meet the requirements for drinking water. The stored rainwater is characterised by low conductivity, hardness and alkalinity compared to mains water. Three widely used bacterial indicators - total coliforms, E. coli and enterococci - were detected in the majority of samples, indicating microbiological contamination of the water. To elucidate factors affecting the rainwater composition, principal component analysis and cluster analysis were applied to the complete data set of 50 observations. Chemical and microbiological parameters fluctuated during the course of the study, with the highest levels of microbiological contamination observed in roof runoffs collected during the summer. E. coli and enterococci occurred simultaneously, and their presence was linked to precipitation. Runoff quality is also unpredictable because it is sensitive to the weather. Cluster analysis differentiated three clusters: ionic composition, parameters linked with the microbiological load and indicators of faecal contamination. In future surveys, parameters from these three groups will be simultaneously monitored to more accurately characterise roof-collected rainwater.     

Phthalates and nonylphenols in urban runoff: Occurrence, distribution and area emission factors

The urban water system is believed to be an important sink for the nonpoint-source pollutants nonylphenols and phthalates. The presence of nonylphenols (NPs), nonylphenol ethoxylates (NPEOs), and eight phthalates was analyzed in urban stormwater and sediment from three catchment areas in Sweden. Emission loads for these substances were then calculated for a specific urban catchment area. In addition, substance distribution in road runoff passing through a sedimentation facility was modeled using a modified QWASI-model for chemical fate. High concentrations of DEHP, DIDP and DINP (≤ 48, 66 and 200 µg/g dw, respectively) as well as nonylphenol mono- and di-ethoxylate (6.6 and 20 µg/g dw, respectively) were found in the sediment. Aqueous concentrations of the pollutants varied considerably; branched NP was detected in concentrations up to 1.2 µg/L, whereas di(2-ethylhexyl) phthalate (DEHP), diisodecyl phthalate (DIDP), and diisononyl phthalate (DINP) were the most frequently detected phthalates in concentrations up to 5.0, 17 and 85 µg/L, respectively. The fate modeling demonstrated that predicted substance levels in water agreed well with measured levels, whereas the modeled sediment levels were underestimated. Calculation of catchment area emission factors from an urban highway environment revealed that as much as 2.1 kg of total phthalates and 200 g of NP and NPEOs may be emitted per hectare and year. The results indicate that all monitored phthalates, branched NPs and lower NPEOs are present in Swedish urban water systems. The long-chain phthalates DIDP and DINP are believed to occur at higher concentrations than other phthalates because of their higher environmental persistence and their increasing use in Sweden.