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.     

核子密度湿度仪在公路工程质量控制中的应用

本文对核子密度湿度仪(以下简称核子仪)快速测定路基或路面材料的密度和含水量,并计算施工压实度作简要介绍,具体阐述挖坑灌砂法同核子仪法的回归分析和核子仪的特性,从而用于正确使用核子仪控制公路工程质量以指导现场施工,并为路用者参考使用。     

The influence of weathering and organic matter on heavy metals lability in silicatic, Alpine soils

We investigated the effect of organic matter and weathering on the lability and solid phase speciation of heavy metals (Cd, Cr, Cu, Ni, Pb, Zn) in two contrasting subalpine regions in the Italian Alps. Cr, Ni and Cu could be linked to weathering. This was not the case for Pb. Since organic matter (OM) influences the solid phase speciation of heavy metals, the total organic C and N content, the C and N content of different density fractions of OM and also of the labile (oxidised by H₂O₂) and stable (H₂O₂-resistant) fractions were determined. Soil OM stocks were high and soils on north-facing slopes had more OM than the south-facing sites to which they were paired. Density measurements and the H₂O₂ fractionation indicated that the higher OM content on north-facing sites was due to an accumulation of weakly degraded organic material. Due to higher weathering intensity on north-facing sites, the abundance of the EDTA-extractable heavy metals was higher than on south-facing sites. All EDTA-extractable heavy metals showed a good correlation to the water-soluble phenolic concentrations which indicates that the metals were probably translocated as metal-organic complexes. Pb and Cu correlate not only to the light (density < 1 g/cm³) and labile, organic fraction but also to the heavy (density > 2 g/cm³) and stable fraction. High-mountain ecosystems like the Alps are sensitive to changing environmental conditions such as global warming. A warmer climate and the more favourable conditions it brings for biological activity, especially at cooler sites, will probably lead in the short- to mid-term to an increased loss of accumulated, weakly degraded OM. As the Pb and Cu content is significantly related to the labile organic matter pools, the risk exists that an increase in OM mineralisation could affect the storage capacity and mobility of these metals in soils.     

Role of biodegradation in the removal of pharmaceutically active compounds with different bulk organic matter characteristics through managed aquifer recharge: batch and column studies

Natural water treatment systems such as bank filtration have been recognized as providing effective barriers in the multi-barrier approach for attenuation of organic micropollutants for safe drinking water supply. In this study, the role of biodegradation in the removal of selected pharmaceutically active compounds (PhACs) during soil passage was investigated. Batch studies were conducted to investigate the removal of 13 selected PhACs from different water sources with respect to different sources of biodegradable organic matter. Neutral PhACs (phenacetine, paracetamol, and caffeine) and acidic PhACs (ibuprofen, fenoprofen, bezafibrate, and naproxen) were removed with efficiencies greater than 88% from different organic matter water matrices during batch studies (hydraulic retention time (HRT): 60 days). Column experiments were then performed to differentiate between biodegradation and sorption with regard to the removal of selected PhACs. In column studies, removal efficiencies of acidic PhACs (e.g., analgesics) decreased under conditions of limited biodegradable carbon. The removal efficiencies of acidic PhACs were found to be less than 21% under abiotic conditions. These observations were attributed to sorption under abiotic conditions established by a biocide (20 mM sodium azide), which suppresses microbial activity/biodegradation. However, under biotic conditions, the removal efficiencies of these acidic PhACs were found to be greater than 59%. This is mainly attributed to biodegradation. Moreover, the average removal efficiencies of hydrophilic (polar) neutral PhACs (paracetamol, pentoxifylline, and caffeine) with low octanol/water partition coefficients (log K_ow less than 1) were low (11%) under abiotic conditions. However, under biotic conditions, removal efficiencies of the neutral PhACs were greater than 98%. In contrast, carbamazepine persisted and was not easily removed under either biotic or abiotic conditions. This study indicates that biodegradation represents an important mechanism for the removal of PhACs during soil passage.     

Integrated ozone and biotreatment of pulp mill effluent and changes in biodegradability and molecular weight distribution of organic compounds

The overall effectiveness of integrating ozonation with biological treatment on the biodegradability enhancement and recalcitrant organic matter (ROM) removal from pulp mill alkaline bleach plant effluent was investigated. Ozonation was performed in a semi-batch bubble column reactor at pH of 11 and 4.5. Batch biological treatment was conducted in shake flasks. Samples obtained during the treatments were monitored for BOD₅, COD, TOC, and molecular weight distribution. At an ozone dosage of 0.7-0.8 mg O₃/mL wastewater, integrated treatment showed about 30% higher TOC mineralization compared to individual ozonation or biotreatment. Ozone treatment enhanced the biodegradability of the effluent (monitored as 21% COD reduction and 13% BOD₅ enhancement), allowing for a higher removal of pollutants. The conversion of high molecular weight (HMW) to low molecular weight (LMW) compounds was an important factor in the overall biodegradability enhancement of the alkaline effluent. The overall biodegradability of the LMW compounds did not change over the course of ozonation, but it increased from 5% to 50% (measured as COD removal) for the HMW portion. Ozonation at pH of 11 was more effective than that at pH of 4.5 in terms of generating more biodegradable compounds.     

Identifying the sources and fate of anthropogenically impacted dissolved organic matter (DOM) in urbanized rivers

Anthropogenic activities have dramatically changed the loads and compositions of dissolved organic matter (DOM) in urbanized streams. In this study, the spatial and temporal variations of DOM in the anthropogenically impacted Zhujiang River were investigated by analyzing the water samples in an upstream, urbanized area and downstream of the rivers on different days of one year. The results indicated that the levels of dissolved organic carbon (DOC) and total phosphorus (TP) were unaffected by seasonal changes, but the specific UV₂₅₄ absorbance (SUVA) values and the total nitrogen (TN) content were greater in the winter than those in the summer. Parallel factor (PARAFAC) analysis of the excitation emission matrices (EEM) revealed the presence of three anthropogenically derived components [tryptophan-like (C1) and tyrosine-like proteins (C3) and anthropogenic humic substances (C5)] in the urbanized rivers, and they had greater seasonal and spatial variability than the terrestrial and microbial humic substances (C2 and C4). Cluster analysis revealed that treated wastewater was an important source of DOM in the urbanized streams. Photodegradation experiments indicated that the DOM in the populous area of the rivers had greater photodegradation potentials than that in the downstream region or in the natural waters. Interestingly, that the anthropogenic humic substances (C5) were considerably more photoreactive than the other four PARAFAC components, which exhibited a decrease of 80% after exposure to sunlight for 0.5 d. This study suggests that the treated wastewater could be an important input to the DOM in the urbanized rivers and the naturally occurring photodegradation could help in eliminating the anthropogenic DOM during their transport.     

Effects of temperature and biodegradable organic matter on control of biofilms by free chlorine in a model drinking water distribution system

This study used annular reactors (AR) to investigate, under controlled laboratory conditions, the effects of temperature and biodegradable organic matter (BOM) on the free chlorine residual needed to control biofilm accumulation, as measured by heterotrophic plate count (HPC) bacteria. Biofilm was grown on PVC coupons, initially in the absence of chlorine, at 6, 12, and 18 degrees C, in the presence and absence of a BOM supplement (250 microg C/L) added as acetate. During the early stages of chlorine addition, when no measurable free chlorine residual was present, a reduction in biofilm HPC numbers was observed. Subsequently, once sufficient chlorine was added to establish a residual, the biofilm HPC numbers expressed as log CFU/cm2 fell exponentially with the increase in free chlorine residual. Temperature appeared to have an important effect on both the chlorine demand of the system and the free chlorine residual required to control the biofilm HPC numbers to the detection limit (3.2 Log CFU/cm2). For the water supplemented with BOM, a strong linear correlation was found between the temperature and the free chlorine residual required to control the biofilm. At 6 degrees C, the presence of a BOM supplement appeared to substantially increase the level of free chlorine residual required to control the biofilm. The results of these laboratory experiments provide qualitative indications of effects that could be expected in full-scale systems, rather than to make quantitative predictions.     

Spatial and seasonal patterns of fluorescent organic matter in Lake Kinneret (Sea of Galilee) and its catchment basin

Lake Kinneret (Sea of Galilee) is one of the major water resources in Israel. The origin and characteristics of natural organic matter (NOM) in the lake and its tributary rivers were studied using fluorescence excitation emission matrices (EEM) and parallel factor analysis. Two humic-like and one proteinous components were sufficient to describe EEM variability among 167 water samples collected between 2/2005 and 9/2006. The two humic-like components showed different relations in lake and riverine samples. Their vertical distribution in the lake was affected by seasonal stratification and distance from water surface, presumably reflecting the release of humic-like matter from sediments, its production via NOM transformation in the bottom layers, and its photodegradation in the upper layers. Vertical distribution of the proteinous component, indicating biological activity at upper water layers, did not correlate with that of the humic-like components. Dissolved organic carbon concentrations did not show any vertical stratification, emphasizing the power of EEM to explore NOM dynamics.