Dissolved organic matter from treated effluent of a major wastewater treatment plant: characterization and influence on copper toxicity

A combination of reverse osmosis (RO) concentration and DAX-8/XAD-4 resin adsorption techniques is used to isolate the various constituents of urban dissolved organic matter (DOM) from inorganic salts. Three fractions: hydrophobic (HPO), transphilic (TPI) and hydrophilic (HPI) accounting respectively for 35%, 20% and 45% of extracted carbon, are isolated from effluents of a major French wastewater treatment plant. This atypical DOC distribution, in comparison with natural water where the HPO fraction dominates, shows the significance of HPI fraction which often gets neglected because of extraction difficulties. A number of analytical techniques (elemental, spectroscopic: UV, FTIR) allow highlighting the weak aromaticity of wastewater effluent DOM (EfOM) due to fewer degradation and condensation processes and the strong presence of proteinaceous structures indicative of intense microbial activity. Copper toxicity in the presence of DOM is estimated using an acute toxicity test on Daphnia Magna (Strauss). Results reveal the similar protective role of each EfOM fraction compared to reference Suwannee river fulvic acid despite lower EfOM aromaticity (i.e. specific UV absorbance). The environmental implications of these results are discussed with respect to the development of site-specific water quality criteria.     

活性焦吸附对反渗透浓水膜蒸馏减排工艺的影响

本研究采用膜蒸馏(MD)技术,对煤化工废水2套处理工艺——(1)"混凝-超滤(UF)-反渗透(RO)工艺"和(2)"混凝-活性焦(AC)吸附-超滤-反渗透工艺"的RO浓水进行浓缩。通过对比分析MD的膜通量、产水水质以及膜污染等指标,重点考察AC吸附预处理对后续MD工艺的影响。结果表明,AC吸附作为前置膜处理工艺,可有效降低污染物在膜表面的沉积,减少膜润湿现象,并提高膜通量。GC-MS分析表明,AC能有效吸附废水中的酮类、醇类、酯类以及杂环类等挥发性有机物,降低MD过程中挥发至产水侧的有机物浓度,从而提高MD产水水质。     

Comprehensive characterization of oil refinery effluent-derived humic substances using various spectroscopic approaches

Refinery effluent-derived humic substances (HS) are important for developing refinery effluent reclamation techniques and studying the environmental chemistry of wastewater effluents. In this study, dissolved organic matter (DOM) from refinery effluent was concentrated using a portable reverse osmosis (RO) system. HS were isolated from RO retentates with XAD-8 resin. A variety of approaches such as specific UV absorbance at 254nm (SUV(254)), elemental analysis, size exclusion chromatography (SEC), solid-state cross polarization magic angle spinning (13)C nuclear magnetic resonance spectrometry ((13)C CPMAS NMR), Fourier transform infrared spectrometry (FTIR), and electrospray ionization/ion trap/mass spectrometry (ESI/ion trap/MS) were employed for characterization of HS. The portable RO system exhibited high yield and recovery of DOM for concentrating refinery effluent. The concentration of dissolved organic carbon (DOC) in the refinery effluent was 9.9mg/l, in which humic acids (HA) and fulvic acids (FA) accounted for 2.3% and 34.6%, respectively. Elemental and SUV(254) analyses indicated relative high amounts of aliphatic structures and low amounts of aromatic structures in refinery effluent-derived HS. Refinery effluent-derived HS displayed lower molecular weight than natural HS. The number-average molecular weight (M(n)) and the weight-average molecular weight (M(w)) of HA were 1069 and 2934, and those of FA were 679 and 1212 by SEC, respectively. By ESI/ion trap/MS, the M(n) and the M(w) of FA were 330 and 383. Four kinds of carbon structures (aliphatic, aromatic, heteroaliphatic, and carboxylic carbons) were found in refinery effluent-derived HS by (13)C NMR analysis. The quantitative results support the interpretation that these HS are rich in aliphatic carbons and poor in aromatic carbons. Proteinaceous materials were identified by FTIR analysis in refinery effluent-derived HS.     

Human pharmaceuticals, antioxidants, and plasticizers in wastewater treatment plant and water reclamation plant effluents.

The primary objective of this study was to determine the presence of unregulated organic chemicals in reclaimed water using complementary targeted and broad spectrum approaches. Eleven of 12 targeted human pharmaceuticals, antioxidants, and plasticizers, and 27 tentatively identified non-target organic chemicals, were present in secondary effluent entering tertiary treatment trains at a wastewater treatment plant and two water reclamation facilities. The removal of these compounds by three different tertiary treatment trains was investigated: coagulant-assisted granular media filtration (California Title-22 water, 22 CCR 60301-60357; Barclay [2006]), lime clarification/reverse osmosis (lime/ RO), and microfiltration-reverse osmosis (MF/RO). Carbamazepine, clofibric acid, gemfibrozil, ibuprofen, p-toluenesulfonamide, caffeine, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), and N-butyl benzenesulfonamide (N-BBSA) were present at low to high nanogram-per-liter levels in Title 22 water. The lime/RO product waters contained lower concentrations of clofibric acid, ibuprofen, caffeine, BHA, and N-BBSA (<10 to 71 ng/L) than their Title 22 counterparts. The MF/RO treatment reduced concentrations to levels below their detection limits, although BHT was present in MF/RO product water from one facility. The presence of the target analytes in two surface waters used as raw drinking water sources and a recharged groundwater was also examined. Surface waters used as raw drinking water sources contained caffeine, BHA, BHT, and N-BBSA, while recharged groundwater contained BHT, BHA, and N-BBSA. Nontarget compounds in recharged groundwater appeared to be attenuated with increased residence time in the aquifer.     

Effects of photodegradation of dissolved organic matter on the binding of benzo(a)pyrene

Dissolved organic matter (DOM) in natural waters can bind various organic pollutants, and the affinity of this binding is strongly influenced by the chemical characteristics of the DOM and water pH. This study examined the effects of photochemically induced alteration of the DOM's chemical properties and water pH on the binding of benzo(a)pyrene (BaP). Time- and pH-series of solar-simulated irradiations were performed on a natural water sample and aqueous DOM solutions prepared from aquatic and soil humic substances. The binding affinity of BaP, expressed as a partition coefficient of a compound to DOM, decreased substantially after the DOM samples were irradiated over environmentally relevant radiation doses and pH ranges. The lowering of the pH due to the photoproduction of acidic products often partly offsets the reduction of the binding affinity caused by direct photoalteration of the DOM's chemical structure. The decrease of the binding affinity, after correction for the photoinduced pH change, was positively correlated with the decrease in the molecular weight and the aromaticity of the DOM in the course of irradiation. Increasing O(2) abundance accelerated the decrease of the binding affinity as a result of enhanced DOM photodegradation. Visible light played a more important role in reducing the molecular weight and aromaticity of the DOM than in reducing the content of dissolved organic carbon (DOC) via photoremineralization while the reverse was true for UV radiation, indicating that photochemical reduction of the binding affinity may occur in natural waters at depths greater than UV radiation can reach. A decrease of the affinity of DOM for binding BaP will increase the free dissolved fraction of BaP and thus its availability and toxicity to aquatic organisms. The results from this study may have similar implications for organic pollutants other than BaP.     

Relative sensitivity of Daphnia magna and Brachionus calyciflorus to five pesticides.

Comparative toxicity of several pesticides, lindane, endosulfan, pentachlorophenol (PCP),3,4-dichloroaniline (DCA) and copper sulphate has been tested to determine their lethality in two species of freshwater invertebrates, Daphnia magna and Brachionus calyciflorus. D. magna was more sensitive than B. calyciflorus to all the toxicants tested except to copper sulphate. DCA was the most toxic compound to D. magna and was followed in order of decreasing toxicity by copper sulphate, PCP, endosulfan and lindane. Copper sulphate was the most toxic chemical tested to the rotifer B. calyciflorus and was followed by PCP, endosulfan, lindane and DCA. The 24 hr LC50 values (mg/L) for D. magna and B. calyciflorus, respectively, were: lindane, 1.64 and 22.5; endosulfan, 0.62 and 5.15; DCA, 0.20 and 61.5; PCP, 0.39 and 2.16; copper sulphate, 0.38 and 0.076.     

Membrane filtration of olive mill wastewater and exploitation of its fractions.

Olive mill wastewater (OMW) produced from small units scattered in rural areas of Southern Europe is a major source of pollution of surface and subsurface water. In the present work, a treatment scheme based on physical separation methods is presented. The investigation was carried out using a pilot-plant unit equipped with ultrafiltration, nanofiltration, and reverse osmosis membranes. Approximately 80% of the total volume of wastewater treated by the membrane units was sufficiently cleaned to meet the standards for irrigation water. The concentrated fractions collected in the treatment concentrates were characterized by high organic load and high content of phenolic compounds. The concentrates were tested in hydroponic systems to examine their toxicity towards undesired herbs. The calculations of the cost of the overall process showed that fixed and operational costs could be recovered from the exploitation of OMW byproducts as water for irrigation and/or as bioherbicides.     

Copper toxicity to different field-collected cladoceran species: intra- and inter-species sensitivity

The acute copper sensitivity of 44 European freshwater cladocerans, from four families (Daphniidae, Bosminidae, Macrothricidae, Chydoridae) and 13 genera (Daphnia, Ctenodaphnia, Ceriodaphnia, Simocephalus, Scapholeberis, Bosmina, Acantholeberis, Alona, Acroperus, Chydorus, Eurycercus, Disparalona and Pleuroxus) were assayed. The 48-h EC(50)s of field-collected organisms tested in reconstituted standard laboratory water ranged from 5.3 to 70.6 mug Cu L(-1). Only among Ctenodaphnia were significant intra-species differences observed. Significant inter-species differences were noted among Alonina and Daphnia. Between all genera tested, a maximum of a 12-fold difference in copper sensitivity was noted. Most animals were more sensitive than a laboratory D. magna clone. A weak non-significant increasing trend was noted between mean cladoceran 48-h EC(50) and ambient copper concentration of the different aquatic systems, suggesting acclimation/adaptation in the field. A positive relationship was also observed between the 48-h EC(50) of the field-collected cladoceran species (without the Chydoridae family) and the size of the organisms.     

Occurrence of pharmaceutically active and non-steroidal estrogenic compounds in three different wastewater recycling schemes in Australia

The discovery that natural and synthetic chemicals, in the form of excreted hormones and pharmaceuticals, as well as a vast array of compounds with domestic and industrial applications, can enter the environment via wastewater treatment plants and cause a wide variety of environmental and health problems even at very low concentrations, suggests the need for improvement of water recycling. Three Australian wastewater recycling schemes, two of which employ reverse osmosis (RO) technology, the other applying ozonation and biological activated carbon filtration, have been studied for their ability to remove trace organic contaminants including 11 pharmaceutically active compounds and two non-steroidal estrogenic compounds. Contaminant concentrations were determined using a sensitive analytical method comprising solid phase extraction, derivatization and GC with MS using selected ion monitoring. In raw wastewater, concentrations of analgesics and non-steroidal anti-inflammatory medications were comparable to those found in wastewaters around the world. Remarkably, removal efficiencies for the three schemes were superior to literature values and RO was responsible for the greatest proportion of contaminant removal. The ability of RO membranes to concentrate many of the compounds was demonstrated and highlights the need for continued research into monitoring wastewater treatment, concentrate disposal, improved water recycling schemes and ultimately, safer water and a cleaner environment.     

微絮凝-微滤用于印染废水回用反渗透预处理的试验研究

采用微絮凝过滤-微滤作为反渗透的预处理工艺,用于印染废水二级生化出水回用深度处理.试验考察了预处理效果、工艺参数和反渗透系统运行情况,分析了膜污染的类型及特点.试验结果表明,微絮凝过滤-微滤作为反渗透的预处理工艺,系统运行稳定,相对于超滤-反渗透的"双膜法"工艺,投资和运行费用相对较低,有推广应用价值.     

Microbial fouling of a reverse osmosis municipal water treatment system

Microbial fouling of a municipal water treatment system using reverse osmosis was investigated. From a combination of growth and molecular assays, it was discovered that the prefilter unit concentrated and facilitated microbial growth, and such growth led to microbial fouling of the reverse osmosis unit. Few cells were observed in the prefilter influent, but substantial microbial contamination was observed in the prefilter effluent, and this correlated with increasing headloss across the prefilter. The effluent caused microbial fouling of the leading elements of the reverse osmosis unit, as determined by reduced permeate flow, analysis of the elements, and assays of the membrane foulant. Both the introduction of microorganisms to the reverse osmosis unit from the prefilter unit and headloss across the prefilter could be effectively controlled through cleansing of the prefilter housing unit with sulfuric acid. Such treatments must be performed at appropriate intervals to prevent subsequent microbial growth in the prefilter unit.     

Study of using microfiltration and reverse osmosis membrane technologies for reclaiming cooling water in the power industry.

A study of using dual membrane technologies, microfiltration (MF) and reverse osmosis (RO), for reclaiming blowdown of the cooling tower was conducted at ZJK power plant, Hebei province, China. The study shows that the combined MF-RO system can effectively reduce water consumption in the power industry. The results indicate that MF process is capable of producing a filtrate suitable for RO treatment and achieving a silt density index (SDI) less than 2, turbidity of 0.2 NTU. The water quality of RO effluent is very good with an average conductivity of about 40 micros/cm and rejection of 98%. The product water is suitable for injection into the cooling tower to counteract with cooling water intrusion. After adopting this system, water-saving effectiveness as expressed in terms of cycles of concentration could be increased from 2.5-2.8 times to 5 times.     

Inter- and intra-species variation in acute zinc tolerance of field-collected cladoceran populations

Acute zinc toxicity was assessed for 10 freshwater cladoceran species collected in six different ecosystems across Europe and for two standard laboratory-reared species (Daphnia magna and Ceriodaphnia dubia). The collected organisms belonged to five different genera: Daphnia (subgenus Daphnia and Ctenodaphnia), Ceriodaphnia, Simocephalus, Acroperus and Chydorus. The 48-h EC50 of the field-collected organisms tested in standard laboratory water ranged from 375+/-141 to 4314+/-1513 microg Znl(-1). The laboratory clone of D. magna was less sensitive than the majority of the field-collected species, while our laboratory Ceriodaphnia dubia was the second most sensitive. Considerable inter-species variation was found within the genus of Ceriodaphnia (factor 6) and within the genus Daphnia (factor 8). Among the different (sub)genera tested, Chydorus and Ctenodaphnia were significantly more tolerant than the others (up to a factor 3 difference). A significant positive relationship (r2=0.67, p<0.05) between the mean cladoceran 48-h EC50 and the ambient zinc concentration of the different aquatic systems was demonstrated, suggesting a role of acclimation and/or adaptation. No significant correlation between the acute zinc tolerance and the length of the organisms was found.     

Rejection of emerging organic micropollutants in nanofiltration-reverse osmosis membrane applications.

The rejection of emerging trace organics by a variety of commercial reverse osmosis (RO), nanofiltration (NF), and ultra-low-pressure RO (ULPRO) membranes was investigated using TFC-HR, NF-90, NF-200, TFC-SR2, and XLE spiral membrane elements (Koch Membrane Systems, Wilmington, Massachusetts) to simulate operational conditions for drinking-water treatment and wastewater reclamation. In general, the presence of effluent organic matter (EfOM) improved the rejection of ionic organics by tight NF and RO membranes, as compared to a type-II water matrix (adjusted by ionic strength and hardness), likely as a result of a decreased negatively charged membrane surface. Rejection of ionic pharmaceutical residues and pesticides exceeded 95% by NF-90, XLE, and TFC-HR membranes and was above 89% for the NF-200 membrane. Hydrophobic nonionic compounds, such as bromoform and chloroform, exhibited a high initial rejection, as a result of both hydrophobic-hydrophobic solute-membrane interactions and steric exclusion, but rejection decreased significantly after 10 hours of operation because of partitioning of solutes through the membranes. This resulted in a partial removal of disinfection byproducts by the RO membrane TFC-HR. In a type-II water matrix, the effect of increasing feed water recoveries on rejection of hydrophilic ionic and nonionic compounds was compound-dependent and not consistent for different membranes. The presence of EfOM, however, could neutralize the effect of hydrodynamic operating condition on rejection performance. The ULPRO and tight NF membranes were operated at lower feed pressure, as compared to the TFC-HR, and provided a product water quality similar to a conventional RO membrane, regarding trace organics of interest.     

Optimization and treatment of wastewater of crude oil desalting unit and prediction of scale formation

In this article, one of Iran’s southwest oil fields that produces 3200 barrels per day (bbl/d) of wastewater from oil and gas processing was investigated. Experimental analysis of oil reservoir water and desalting wastewater disposal of crude oil desalting unit was performed. First, water was treated with a reverse osmosis membrane. As a result, the purified water, with lower total dissolved solids (TDS) and pH, was a suitable candidate for injection into the adjacent wells of the crude oil desalting unit. The effectiveness and compatibility of this wastewater to the formation water of the oil field wells were simulated. Finally, we studied and identified the formation, the amount, and the type of mineral scale deposits. These are the most important problems during water injection into the wells. The analysis shows that the refined water from the reverse osmosis (RO) process was a suitable and low-cost economical option for injection in onshore and offshore fields, due to the low amount of salts, the concentration of susceptible ions in scaling formation, and the appropriate pH. This oil field, which is in the second half of life, requires enhanced oil recovery methods (EOR) for the maintenance of pressure and an increase in oil recovery.

     

反渗透处理稀土氨氮废水试验研究

根据稀土冶炼厂排放的碳铵沉淀洗涤废水的水质情况,采用NH4Cl和 NaCl模拟废水进行了反渗透可行性对比实验。模拟实验发现,在相同条件下反渗透对NaCl 较NH₄Cl 有着更高的去除率,而NH₄Cl 相对NaCl则有着更高的产水速率。实际废水试验结果表明,在恒定操作压力范围内回收率为65%的条件下,NH₄Cl浓度为2.85 g/L的碳铵沉淀洗涤废水经反渗透处理其NH₄Cl去除率为77.3%,可作为氨氮废水的预处理。对该废水处理成本进行了分析,得出其约为2.7元/m³,比相近浓度氨氮废水的氨吹脱处理成本节省约26%。     

Chronic toxicity tests with Daphnia magna for examination of river water quality

Chronic toxicity tests with Daphnia magna were applied for examination of river water quality. Water was sampled from the Maioka River in Yokohama City on May 14, 20, and 27, 1999, and used for the test after solid-phase extraction. The chronic test was carried out according to the OECD method. The duration was 21 days and the total number of live offspring produced per parent animal was counted. The results of the tests showed, survival rates of 100% using river water sampled on May 14 and 20 and the total numbers of live offspring produced per parent animal did not differ from the control. However, the survival rate of the sample collected on May 27 was 0% and the pesticides, fenitrothion, and thiobencarb were detected in the water. In addition to the river water samples, reconstituted water (Elendt M7) with additions of fenitrothion and thiobencarb was prepared to investigate mortality. When the reconstituted water with thiobencarb was applied to the test, the total number of live offspring produced per parent animal did not differ from the control. In contrast, when reconstituted water with fenitrothion was applied to the test, most parents were alive, but the total number of live offspring produced per parent animal was apparently different. The results of the above tests indicate that D. magna was affected not only by fenitrothion in the river water collected on May 27, but also by other factors that were not clarified in this study.     

Assessing demineralization treatments for PVC effluent reuse in the resin polymerization step

To reduce fresh water consumption in a polyvinyl chloride (PVC) plant, the effluent from a biological treatment must be demineralized to be re-used in the resin polymerization process. Demineralization is a critical process, since the quality and the stability of the PVC resins are highly influenced by the water quality used in the process. The main target values for water parameters are the following: conductivity <10 μScm^?1, TOC < 10 mg L^?1, and Al < 0.1 mg L^?1. To achieve this quality, several reverse osmosis membranes from different materials and suppliers were tested and compared in the demineralization treatment. Polyamide membranes showed higher salt rejection compared to cellulose acetate membranes yielding both types similar flux and permeability. Two-pass reverse osmosis treatment was necessary to reach conductivities lower than 10 μS cm^?1. On the other hand, a good quality effluent for reuse was obtained by combining RO and ionic exchange resins. Results showed that good quality PVC resins in terms of color, granulometry, porosity, and bulk density were obtained when demineralized water from two-pass reverse osmosis was used as fresh water, proving the feasibility of the effluent reuse in the PVC industry.     

A freshwater shrimp (Paratya compressa improvisa) as a sensitive test organism to pesticides

The susceptibility of 2-week-old individuals of the freshwater shrimp, Paratya compressa improvisa, to five kinds of insecticide and five kinds of herbicide was examined in comparison with that of two species of Cladocera, Daphnia magna and Moina macrocopa. The shrimp was especially sensitive to two organophosphorus insecticides. The 48-h LC50 values for fenitrothion and fenthion to the shrimp were 1.15 and 1.04 microg litre(-1) (mean value, n=2), in contrast with 37.8 and 35.3 microg litre(-1) in the case of M. macrocopa, and more than 50 microg litre(-1) with D. magna. The shrimp also showed the higher susceptibility to other insecticides, diazinon, carbaryl (NAC) and BPMC, apart from D. magna to diazinon and NAC. The shrimp also showed higher susceptibility to herbicides. The 48-h LC50 values of CNP, benthiocarb, oxadiazon, butachlor, and symetryne to the shrimp were two to eight times lower than those of two species of Cladocera, except for the LC50 value of oxadiazon to M. macrocopa, which was very slightly higher. However, the shrimp showed a somewhat lower susceptibility to heavy metals than the two species of Cladocera, especially to copper, and to cadmium and zinc in comparison with D. magna. A bioassay using the shrimp with river water, collected from the river adjacent to the paddy field, showed clearly the high mortality of the shrimp following the aerial spraying with pesticides.