Occurrence and fate of bulk organic matter and pharmaceutically active compounds in managed aquifer recharge: a review

Managed aquifer recharge (MAR) is a natural water treatment process that induces surface water to flow in response to a hydraulic gradient through soil/sediment and into a vertical or horizontal well. It is a relatively cost-effective, robust and sustainable technology. Detailed characteristics of bulk organic matter and the occurrence and fate of pharmaceutically active compounds (PhACs) during MAR processes such as bank filtration (BF) and artificial recharge (AR) were reviewed. Understanding the fate of bulk organic matter during BF and AR is an essential step in determining pre- and/or post-treatment requirements. Analysis of organic matter characteristics using a suite of analytical tools suggests that there is a preferential removal of non-humic substances during MAR. Different classes of PhACs were found to behave differently during BF and AR. Antibiotics, non-steroidal anti-inflammatory drugs (NSAIDs), beta blockers, and steroid hormones generally exhibited good removal efficiencies, especially for compounds having hydrophobic-neutral characteristics. However, anticonvulsants showed a persistent behavior during soil passage. There were also some redox-dependent PhACs. For example, X-ray contrast agents measured, as adsorbable organic iodine (AOI), and sulfamethoxazole (an antibiotic) degraded more favorably under anoxic conditions compared to oxic conditions. Phenazone-type pharmaceuticals (NSAIDs) exhibited better removal under oxic conditions. The redox transition from oxic to anoxic conditions during soil passage can enhance the removal of PhACs that are sensitive to redox conditions. In general, BF and AR can be included in a multi-barrier treatment system for the removal of PhACs.     

Removal of bulk dissolved organic carbon (DOC) and trace organic compounds by bank filtration and artificial recharge

Bank filtration and artificial recharge provide an important drinking water source to the city of Berlin. Due to the practice of water recycling through a semi-closed urban water cycle, the introduction of effluent organic matter (EfOM) and persistent trace organic pollutants in the drinking water is of potential concern. In the work reported herein, the research objectives are to study the removal of bulk and trace organics at bank filtration and artificial recharge sites and to assess important factors of influence for the Berlin area. The monthly analytical program is comprised of dissolved organic carbon (DOC), UV absorbance (UVA254), liquid chromatography with organic carbon detection (LC-OCD), differentiated adsorbable organic halogens (AOX) and single organic compound analysis of a few model compounds. More than 1 year of monitoring was conducted on observation wells located along the flowpaths of the infiltrating water at two field sites that have different characteristics regarding redox conditions, travel time, and travel distance. Two transects are highlighted: one associated with a bank filtration site dominated by anoxic/anaerobic conditions with a travel time of up to 4-5 months, and another with an artificial recharge site dominated by aerobic conditions with a travel time of up to 50 days. It was found that redox conditions and travel time significantly influence the DOC degradation kinetics and the efficiency of AOX and trace compound removal.     

Vulnerability of bank filtration systems to climate change

Bank filtration (BF) is a well established and proven natural water treatment technology, where surface water is infiltrated to an aquifer through river or lake banks. Improvement of water quality is achieved by a series of chemical, biological and physical processes during subsurface passage. This paper aims at identifying climate sensitive factors affecting bank filtration performance and assesses their relevance based on hypothetical ‘drought’ and ‘flood’ climate scenarios. The climate sensitive factors influencing water quantity and quality also have influence on substance removal parameters such as redox conditions and travel time. Droughts are found to promote anaerobic conditions during bank filtration passage, while flood events can drastically shorten travel time and cause breakthrough of pathogens, metals, suspended solids, DOC and organic micropollutants. The study revealed that only BF systems comprising an oxic to anoxic redox sequence ensure maximum removal efficiency. The storage capacity of the banks and availability of two source waters renders BF for drinking water supply less vulnerable than surface water or groundwater abstraction alone. Overall, BF is vulnerable to climate change although anthropogenic impacts are at least as important.     

多维反滤回灌井室内稳定流试验研究

反滤回灌井是山东胶东半岛地下水回灌中常用的回灌设施,它由普通回灌井和回灌池组成。在分析现有反滤回灌井存在问题的基础上,设计了一组回灌量大,又能防淤积、防低水位污水回灌、抗水流冲刷的多维反滤回灌井,给出了单井回灌量的理论计算公式和计算参数;同时,研制了室内稳定流回灌试验装置,进行了普通回灌井、现有反滤回灌井和多维反滤回灌井的室内稳定流试验研究,得出结论:1同现有反滤回灌井相比,多维反滤回灌井的单井回灌量增加了370%~420%;2多维回灌井口的形状影响单井回灌量,在过水断面面积相同的情况下,圆形多维回灌井口的单井回灌量最大;3初次回灌试验中,单井回灌量最大,随回灌试验次数增加,单井回灌量逐渐减小,并趋向于稳定;4单井回灌量与多维回灌井口过水断面开孔率是一个非线性的关系,20%的过水断面开孔率是适宜的。研究成果对于提高反滤回灌井的回灌能力和定量计算单井回灌量具有重要的现实意义。     

Grundwasserfauna als Indikator für Oberflächenwasser-Grundwasser-Interaktionen im Bereich einer Uferfiltrationsanlage

The water quality of bank filtrate is strongly influenced by complex hydrological exchange processes. In particular, surface water coming into contact with groundwater is a potential hazard for drinking water quality. Therefore monitoring for surface water intrusion is required for assuring the quality of the raw water being used. The hydrological interactions of the Rhine bank filtration site at Flehe, Duesseldorf were analyzed hydro-chemically and faunistically and both approaches were compared. In addition, the degree of surface water influence was determined by using the fauna and the Groundwater-Fauna-Index (GFI) after Hahn (2006a). The fauna provided a more detailed impression of the hydrological situation of the study area than the water chemistry. By means of the fauna and the GFI, different groundwater types were identified, indicating different degrees of surface water intrusion. Thus, the fauna and the GFI are considered to be suitable measures for the assessment of the hydrological conditions as well as for the evaluation of the surface water impact on the groundwater and consequently are suitable for use in vulnerability assessment.     

水源热泵系统回灌量衰减的监测与分析

为了解决水源热泵系统回灌过程中出现的问题,选择典型项目开展回灌监测工作,通过对各井水位、水量的监测,获得了7年的监测数据,确定了各井的回灌能力,监测结果表明:项目运行的前3年回灌系统处于最佳工作状态,但系统运行6年后,各井回灌量累计衰减超过60%。     

Biodegradable fraction of organic carbon estimated under oxic and anoxic conditions

The biodegradability of water samples is usually estimated with bioassays under oxic conditions. In order to overcome some of the drawbacks linked to the incubation of the samples in aerobic batches, a new protocol is proposed and tested, which is based on an organic carbon (OC) balance after a 45 days incubation under anoxic conditions with excess nitrate. The biodegradable fractions of organic matter obtained with the anoxic protocol are slightly lower than those obtained under oxic conditions. Several possible reasons for a systematic underestimation of the biodegradable organic matter under anoxic conditions are evaluated and discussed: a reduced microbial metabolic potential, significantly reduced degradation rates for the slowly biodegradable organic matter, an additional production of refractory organic compounds during the incubation, or the inhibition of the recycling of the organic matter stored in bacterial biomass. Nevertheless, the 7% difference observed on the biodegradable total OC estimations keeps low enough so that the anoxic protocol can be proposed as a convenient alternative to the oxic one.     

Nutrient cycling at the sediment-water interface and in sediments at Chiricahueto marsh: a subtropical ecosystem associated with agricultural land uses

A study was conducted to examine the potential role to accumulate and transform nitrogen and phosphorus of a common wetland type marsh; the site is located in a subtropical environment that receives agricultural pollutants. Chiricahueto marsh effectively removes N and P from surface waters. It is clear that the diagenetic processes are mainly controlled by the exponential decomposition of organic matter that takes place at the sediment-water interface and in the sedimentary column, under oxic and suboxic-anoxic conditions, respectively. Mass balances indicated a net sedimentation of 11.3 g Nm(-2)x yr (-1) and 3.9 g Pm(-2) x yr (-1), which results in an annual regeneration of 1.7 g Nm(-2) and 0.8 g Pm(-2) at the sediment-water interface under oxic conditions. A major remineralization rate was estimated in 6.4 g Nm(-2) x yr (-1) and 1.1g Pm(-2) x yr (-1) into the sedimentary column where suboxic to anoxic conditions occur by the utilization of nitrate, Fe and Mn as electron acceptors. The estimated burial fluxes in the deeper sediments (>50 cm) were 1.5 g Nm(-2) x yr (-1) and 0.4 g Pm(-2) x yr (-1).     

Fate of N-nitrosodimethylamine in recycled water after recharge into anaerobic aquifer

Laboratory and field experiments were undertaken to assess the fate of N-nitrosodimethylamine (NDMA) in aerobic recycled water that was recharged into a deep anaerobic pyritic aquifer, as part of a managed aquifer recharge (MAR) strategy. Laboratory studies demonstrated a high mobility of NDMA in the Leederville aquifer system with a retardation coefficient of 1.1. Anaerobic degradation column and ¹⁴C-NDMA microcosm studies showed that anaerobic conditions of the aquifer provided a suitable environment for the biodegradation of NDMA with first-order kinetics. At microgram per litre concentrations, inhibition of biodegradation was observed with degradation half-lives (260 ± 20 days) up to an order of magnitude greater than at nanogram per litre concentrations (25-150 days), which are more typical of environmental concentrations. No threshold effects were observed at the lower ng L⁻¹ concentrations with NDMA concentrations reduced from 560 ng L⁻¹ to <6 ng L⁻¹ over a 42 day ¹⁴C-NDMA aerobic microcosm experiment.Aerobic ¹⁴C-NDMA microcosm studies were also undertaken to assess potential aerobic degradation, likely to occur close to the recharge bore. These microcosm experiments showed a faster degradation rate than anaerobic microcosms, with a degradation half-life of 8 ± 2 days, after a lag period of approximately 10 days.Results from a MAR field trial recharging the Leederville aquifer with aerobic recycled water showed that NDMA concentrations reduced from 2.5 ± 1.0 ng L⁻¹ to 1.3 ± 0.4 ng L⁻¹ between the recharge bore and a monitoring location 20 m down gradient (an estimated aquifer residence time of 10 days), consistent with data from the aerobic microcosm experiment. Further down gradient, in the anaerobic zone of the aquifer, NDMA degradation could not be assessed, as NDMA concentrations were too close to their analytical detection limit (<1 ng L⁻¹).     

234U/238U isotope ratios in groundwater from Southern Nevada: a comparison of alpha counting and magnetic sector ICP-MS

The 234U/238U activity ratio (AR) is extensively used as a geochemical tool to investigate movement and flow relationships in major hydrological units, information that is particularly important when considering nuclear waste disposal. It is usually determined by radiochemical separation and concentration of U, followed by energy-specific alpha particle counting. Alternatively, sector field inductively coupled plasma mass spectrometry (SF-ICP-MS) can be used to measure U isotopic signatures directly in groundwater samples. Here, we compare the two methods for samples of spring and groundwater from southern Nevada. Results for samples stripped from stainless steel disks, previously used for alpha counting, and for splits of groundwater samples show good agreement between the methods. However, SF-ICP-MS is faster, requires much less sample, and produces essentially no waste. We demonstrate applicability of the SF-ICP-MS method for groundwater collected from over 25 wells on and near the Nevada Test Site during 2003. Uranium concentrations ranged from 0.17 to 9.87 ppb with a mean of 2.9 ppb, while 234U/238U AR values ranged from 1.9 to 11.5 with a mean of 4.3. Groundwater collected from deep wells in the northern part of the study area tended to have moderate to high U concentrations and AR values, possibly representative of older volcanic-type waters, whereas groundwater from wells in the Fortymile Wash area had relatively low AR and U concentrations, suggesting younger waters with a possible local recharge component.     

Identification and significance of sulphonamides (p-TSA, o-TSA, BSA) in an urban water cycle (Berlin, Germany)

Because of the nature of the water cycle in Berlin, a number of persistent wastewater residues are present in the surface water and may potentially reach the groundwater via bank filtration and artificial recharge. The occurrence and behaviour of the wastewater residues para-toluenesulphonamide (p-TSA), ortho-toluenesulphonamide (o-TSA) and benzenesulphonamide (BSA) through wastewater treatment, surface water, bank filtration and drinking water treatment was studied. In addition, groundwater below a former sewage farm was investigated. All three compounds are ubiquitous in the aquatic environment of Berlin. p-TSA concentrations are much higher than those of o-TSA and BSA. p-TSA was found in high concentrations in the wastewater influent (2 to 15microg/L), in the wastewater effluent (<0.15 to 2.34microg/L) and in sewage farm groundwater (<0.05 to 20microg/L) and in lower concentrations in the surface water (<0.05 to 1.15microg/L), bank filtrate (<0.05 to 0.30microg/L) and drinking water (<0.05 to 0.54microg/L). p-TSA is considerably depleted during waste- and drinking water treatment ( approximately 90% reduction each). The concentration ranges for o-TSA and BSA in wastewater influents were 0.11 to 8microg/L and <0.05 to 0.64microg/L, respectively, while the values for wastewater effluents were 0.14 to 4microg/L for o-TSA and 0.25 to 0.49microg/L for BSA. Wastewater treatment and drinking water treatment do not reduce the concentrations of o-TSA and BSA. The behaviour of o-TSA during wastewater treatment varies largely between different wastewater treatment plants where concentrations increase, remain constant or decrease. BSA forms during treatment. The concentrations measured in surface water, sewage farm groundwater, bank filtrate and drinking water were <0.05 to 1.74microg/L for o-TSA and <0.05 to 0.53microg/L for BSA.     

水源热泵系统抽灌井常压、加压回灌试验

以某高校水源热泵系统2口地热水井（1抽1灌）为研究对象,采取回灌井回扬,对回灌井的常压回灌、加压回灌的效果进行了试验分析,探讨了回灌的技术要点,介绍了该工程地热水井实际的运行情况。     

Phosphorous retardation and breakthrough into well water in a soil-aquifer treatment (SAT) system used for large-scale wastewater reclamation

Retardation and breakthrough of phosphorous in the soil/sediment profiles of a SAT system at the Shafdan wastewater treatment plant, Israel, were investigated in situ. Area-weighted average effluent load to the whole site was 65 m yr(-1). Annual average concentrations of P in the recharged effluent ranged between about 1.5 and 7.7 mg L(-1) during 25 yr of operation, while P in groundwater remained 40 m sandy soil/sediment formations. By combining results of isotherm tests, long-term monitoring of phosphorous (P) in solid and liquid phases of the recharge site, a simple multi-cell tracer-movement model and measured chloride breakthrough curves to the groundwater we calculated P distribution coefficients and estimated the retardation factor of P. Laboratory measured, isotherm-based distribution coefficient, Kd(I), was about 4-6 L kg(-1) at equilibrium P concentration <6 mg L(-1), while field-based Kd(F) was considerably higher, reaching about 20-55 L kg(-1) after a load of around 1800 m effluent was recharged. Measured P breakthrough times into two shallow observation wells were 19-21 yr. Calculated P breakthrough times using Kd(F) data agreed with observations while those calculated using Kd(I) grossly underestimated retardation and predicted much shorter breakthrough times. This validated the approach and model used. Estimated P breakthrough times to the deeper observation wells and the recovery wells are more than 100 yr and 400-1100 yr, respectively. These estimates show that P contamination of the reclaimed effluents in the Shafdan plant will not be a problem in the foreseeable future.     

Polar nitrogen compounds and their behaviour in the drinking water treatment process

Aliphatic and alicyclic amines as well as ethanolamines are extremely polar compounds, frequently found in the environment, and some of them have high toxicity. To address the contamination of selected German surface waters examined and the importance of bank filtration in Eastern Germany, investigations on the behaviour of polar organic nitrogen compounds during water treatment were carried out. Test conditions were designed appropriately for drinking water treatment conditions, and the tests were carried out using model water as well as bank filtrate. Test filter studies of microbial degradation of selected compounds demonstrated the following order of biodegradability: ethanolamine > dimethylamine > pyrrolidine > ethylenediamine. piperidine > diethylamine > morpholine > piperazine > cyclohexylamine. Flocculation tests using iron salts as well as aluminium salts as coagulants showed very low removal rates for the amines. The best results for the removal of the polar organic nitrogen compounds from the water were obtained using ozonation. Based on the reaction-rate constants, the order of degradation by ozone is: piperazine > morpholine > ethylenediamine > piperidine, cyclohexylamine > dimethylamine > ethanolamine > pyrrolidine > diethylamine. Disinfection by chlorine-containing agents under drinking water treatment conditions did not give effective elimination of the selected polar nitrogen compounds.     

Fate of trace organics during rapid infiltration of primary wastewater at Fort Devens, Massachusetts

Transport and fate of trace organics were studied during rapid infiltration of primary wastewater at a land application facility in Fort Devens, Massachusetts. A preliminary sampling trip was made to compare trace organic concentrations in the infiltrating wastewater and in ground water samples from three monitoring wells around the site. Trace organic concentrations were reduced by the rapid infiltration process. However, significant concentrations of specific compounds could be detected in ground water down-gradient of the site.Therefore, a field study was undertaken to determine the primary region where trace organics were removed in the system. Teflon monitoring wells were installed at a depth of 1.2 m in one of the basins at the site prior to flooding. Flooding was initiated and samples of the raw wastewater, the wastewater entering the basin, the infiltrate at 1.2-m depth and the ground water down-gradient of the site were analyzed for six compounds selected for the study.Results from replicate samples during the 6-day flooding period demonstrated that most of the removal for the six compounds occurred in the top meter of the soil, although concentrations of each compound increased substantially in the basin infiltrate from two of the sample points after the fourth day of flooding. No removal of p-dichlorobenzene, p-(I,1,3,3-tetramethylbutyl)phenol and 2-(methylthio)benzothiazole was apparent in the aquifer itself, as indicated by relatively high concentrations of these compounds in the contaminated monitoring well down-gradient of the site.These data indicate that trace organic concentrations in primary effluent can be reduced by rapid infiltration and that most of the removal occurs in the top meter of the soil during the early phase of the flooding cycle. This removal capability can rapidly diminish, however, and result in ground water contamination by trace organics above background levels.     

Impact of solids residence time on biological nutrient removal performance of membrane bioreactor

Impact of long solids residence times (SRTs) on nutrient removal was investigated using a submerged plate-frame membrane bioreactor with anaerobic and anoxic tanks. The system was operated at 10, 25, 50 and 75 days SRTs with hydraulic retention times (HRTs) of 2 h each for the anaerobic and anoxic tanks and 8 h for the oxic tank. Recirculation of oxic tank mixed liquor into the anaerobic tank and permeate into the anoxic tank were fixed at 100% each of the influent flow. For all SRTs, percent removals of soluble chemical oxygen demand were more than 93% and nitrification was more than 98.5% but total nitrogen percent removal seemed to peak at 81% at 50 days SRT while total phosphorus (TP) percent removal showed a deterioration from approximately 80% at 50 days SRT to 60% at 75 days SRT. Before calibrating the Biowin^® model to the experimental data, a sensitivity analysis of the model was conducted which indicated that heterotrophic anoxic yield, anaerobic hydrolysis factors of heterotrophs, heterotrophic hydrolysis, oxic endogenous decay rate for heterotrophs and oxic endogenous decay rate of PAOs had the most impact on predicted effluent TP concentration. The final values of kinetic parameters obtained in the calibration seemed to imply that nitrogen and phosphorus removal increased with SRT due to an increase in anoxic and anaerobic hydrolysis factors up to 50 days SRT but beyond that removal of phosphorus deteriorated due to high oxic endogenous decay rates. This indirectly imply that the decrease in phosphorus removal at 75 days SRT may be due to an increase in lysis of microbial cells at high SRTs along with the low food/microorganisms ratio as a result of high suspended solids in the oxic tank. Several polynomial correlations relating the various calibrated kinetic parameters with SRTs were derived. The Biowin^® model and the kinetic parameters predicted by the polynomial correlations were verified and found to predict well the effluent water quality of the MBR at 35 days SRT.     

Influence of nanoscale zero-valent iron on geochemical properties of groundwater and vinyl chloride degradation: A field case study

A 200 m² pilot-scale field test successfully demonstrated the use of nanoscale zero-valent iron (NZVI) for effective remediation of groundwater contaminated with chlorinated organic compounds in Taiwan within six months. Both commercially available and on-site synthesized NZVI were used. A well-defined monitoring program allowing to collect three-dimensional spatial data from 13 nested multi-level monitoring wells was conducted to monitor geochemical parameters in groundwater. The degradation efficiency of vinyl chloride (VC) determined at most of monitoring wells was 50-99%. It was found that the injection of NZVI caused a significant change in total iron, total solid (TS) and suspended solid (SS) concentrations in groundwater. Total iron concentration showed a moderate and weak correlation with SS and TS, respectively, suggesting that SS may be used to indicate the NZVI distribution in groundwater. A decrease in oxidation-reduction potential (ORP) values from about −100 to −400 mV after NZVI injection was observed. This revealed that NZVI is an effective means of achieving highly reducing conditions in the subsurface environment. Both VC degradation efficiency and ORP showed a correlative tendency as an increase in VC degradation efficiency corresponded to a decrease of ORP. This is in agreement with the previous studies suggesting that ORP can serve as an indicator for the NZVI reactivity.     

Einsatz von Direct Push im Rahmen von Sanierungsuntersuchungen – Fallbeispiel Elsterwerda (Brandenburg)

Monitoring of ground water for remediation projects is usually done using conventional ground water sampling. However, vertical variations in hydrochemistry cannot be detected well with this approach and, as a result, can create serious problems. Such problems were observed at the Elsterwerda site in Brandenburg where a spill of about 470 t of unleaded gasoline contaminated the Quaternary aquifer in 1997. Despite the installation of an increasing number of monitoring wells during site remediation, evaluation of the spatial development of the plume was not possible. Direct Push ground water sampling was therefore used to obtain depth-dependent hydrochemistry information for the design of additional monitoring wells. A mobile gas chromatograph enabled an adaptive site investigation that allowed on-site determination of the appropriate depths and lengths of the screened intervals for small-diameter multichannel monitoring wells. The installation of these multichannel wells provided reproducible, depth dependent information on site hydrochemistry. The investigations at the Elsterwerda site demonstrated the power of direct push technology and showed that simple cleaning of the Direct Push rods and the use of a new sampling tube for each profile eliminates potential cross contamination.     

软土深基坑单井回灌参数优化与现场测试分析

为解决因深基坑降水和基坑渗漏引起的地表沉降问题,通常在坑外进行地下水回灌,而回灌参数会影响地表沉降控制效果。为了选取合适的回灌参数,采用ABAQUS有限元程序进行滤管长度、回灌井井径、井深、回灌压力对地表沉降影响的敏感性分析,得到如下结论:回灌压力和回灌井井深为控制地表沉降的关键因素,对控制基坑周边的沉降变形相对敏感,在设计回灌井时应首先考虑;而滤管长度和回灌井井径对控制地表沉降变形不敏感。回灌压力越大,控制地表沉降的效果越好,但不能无限制增加回灌压力,应根据回灌井周围密封强度计算回灌压力上限值。回灌井越深,基坑周边地表沉降越小,但应结合地质条件选取合理的井深。将选取的回灌参数用于现场回灌试验,回灌后坑外地下水位明显抬升,有效地控制了基坑周边地表沉降。     

咸阳市地热开发与回灌

根据回灌试验井WH1号的相关情况并结合目前国内外回灌经验,介绍回灌机理,并以开采的25口地热井参数均值为标准,对开采井和回灌井的经济效益进行评估,从而达到采灌平衡的模式。