Chemical modifications of groundwater contaminated by recharge of treated sewage effluent

Long-term monitoring of the chemical composition of recharge sewage effluent and associated contaminated groundwater from the Dan Region Sewage Reclamation Project shows, after 16 years of recharge operation, the presence of a distinct saline plume (up to 400 mg/l Cl), extending 1600 m downgradient in the Coastal Plain aquifer of Israel. The recorded electrolyte composition of groundwater in the vicinity of the recharge area reflects the variations in the compositions of the sewage effluents, as well as water-rock interactions induced by the recharge of treated sewage effluents. The original sewage composition was modified, particularly during early stages of effluent migration in the unsaturated zone, by cation-exchange and adsorption reactions. Since the soil sorption capacity is finite these reactions caused only limited modifications, and once the system reached a steady state the inorganic composition of the contaminated groundwater became similar to that of the recharge water. Decomposition of organic matter in the unsaturated zone resulted in CO₂ generation and dissolution of CaCO₃ minerals in the aquifer. It was shown that chemical and/or bio-degradation of organic matter takes place mainly in the unsaturated (vadose) zone. Hence, monitoring the efficiency of the vadose zone to retain contaminants is essential for evaluating the quality of groundwater since it was shown that organic compounds behave almost conservatively once the effluents enter and flow within the saturated zone.     

Determination of fluoroquinolone antibiotics in wastewater effluents by liquid chromatography-mass spectrometry and fluorescence detection

The occurrence of quinolone antibiotics (QAs) was investigated in wastewater effluents and surface river/lake waters in the US and Canada by using solid-phase extraction with mixed phase cation exchange disk cartridge and liquid chromatography-mass spectrometry (LC-MS) and liquid chromatography fluorescence detection (LC-FLD). Ofloxacin (OFL) was detected in secondary and final effluents of a wastewater treatment plant (WWTP) in East Lansing, Michigan, at concentrations of 204 and 100 ng/l, respectively. The mass flow calculation, estimated by multiplying the OFL concentration in the final effluent by the average influent volume of the WWTP, showed that the discharge of OFL to the river was 4.8 g/day. The OFL concentrations in wastewater effluents measured in this study are comparable to or less than those observed in several European countries. QAs were not detected in river and lake waters analyzed in this study, which may due to dilution effects and to the higher detection limits, relative to those reported previously. OFL concentrations were approximately 1-2 orders of magnitude lower than the EC50 concentrations for environmental bacterium. However, greater concentrations of other QAs in sewage sludge from WWTPs may result in cumulative effects. Considering that the sewage sludge is applied to the land as fertilizers, soil-dwelling organisms could experience greater exposures to such antibiotics. Monitoring studies of QAs in sewage from WWTPs and in sediment/soil near aquaculture facilities and livestock farms will be necessary for the evaluation of the environmental distribution and risk of these compounds.     

Evaporation behaviour of different organic effluents from open surfaces

Production of large quantities of effluents from different industrial units and the problems of their disposal necessitated this evaporation study. The evaporation of water, sewage water, oil refinery effluent, papermill effluent and liquor distillery effluent was observed in glass beakers when placed (i) in an oven at 60 degrees C and (ii) in screen house for 30 days, by periodically weighing of the beakers. In other experiments, the effect of increasing the frequency of stirring on increasing the evaporation efficiency of the liquor distillery effluent (ELD) was examined in detail. All of the organic effluents except ELD had similar evaporation behaviours as water, but formation of a self-forming film caused the evaporation of ELD to be considerably lower. Resistance to evaporation caused by this film was found to be a decreasing function of the frequency of stirring. This study has a bearing on improving the efficiency of evaporation lagoons, and three stirrings in a day with a manually drawn stirrer in a full-scale lagoon are proposed as a practical and economically viable technique to save 44% of lagoon land in arid and semi-arid regions of the world.     

The cytotoxic and genotoxic potential of surface water and wastewater effluents as determined by bioluminescence, umu-assays and selected biomarkers

Two bacterial tests employing Photobacterieum phosphoreum (Microtox bioluminescence test) and Salmonella typhimurium TA 1535 pSK1002 (umu-assay) were evaluated to estimate the cytotoxic and genotoxic potential of water samples from the selected rivers in Germany as well as the primary and secondary effluents of some sewage treatment plants. Rainbow trout (Onchorynchus mykiss) were exposed to different concentrations (20-40%) of secondary effluent in the model online aquatic monitoring plant WaBoLu-Aquatox. The toxic potential of water samples from the exposure tanks was determined in two prokaryotic test systems and the biomarkers acethylcholinesterase (AChE) activity in muscle tissue and DNA unwinding assay in liver tissue of fish. Samples from the tested rivers showed no inhibition of the bioluminescence of P. phosphoreum or growth of umu-bacteria. Only primary effluent samples from the treatment plants at the Saale River inhibited the light emission or the growth of test bacteria by more than 20%. The induction ratio of umu-bacteria was in most of the river samples less than the threshold for genotoxicity (IR < 1.5). Only some samples from the Saale River, especially at sites downstream of secondary effluents caused genotoxic responses in the umu-assay. Samples of primary effluents contained the greatest genotoxic potential up to GEUI = 6 which was not detectable in samples of secondary effluents. A concentration range 20-40% secondary effluent inhibited AChE activity in muscle tissue and significantly increased DNA fragmentation in liver tissue of rainbow trout. In contrast, no cytotoxic or genotoxic responses in the umu-assay were caused by water samples. Both bacterial methods can be successfully used to analyse the cytotoxic and genotoxic response of industrial and domestic wastewater and to estimate the effectiveness of sewage treatment units. However, because of their low sensitivity and high susceptibility, they are not reliable as a single test for the detection of cytotoxicity and genotoxicity in surface water. The application of prokaryotic tests systems with biomarkers such as AChE activity and DNA fragmentation in different tissues of test organisms seems to be a useful combination for the assessment of cytotoxic and genotoxic potential in surface water and secondary effluent.     

Removal of two cationic dyes from a textile effluent by filtration-adsorption on wood sawdust

BACKGROUND: Wastewater from textile industry contains various contaminants such as dyes, surfactants and heavy metals. Textile dyes have synthetic origin and complex aromatic molecular structures that make them difficult to biodegrade when discharged in the ecosystem. The objective of this study was to examine the decolourisation of textile effluents containing cationic dyes by filtration-adsorption on wood sawdust from two different origins; fir as an example of a conifer tree, and beech as an example of a deciduous one, and to explain the adsorption mechanism. METHODS: The process of dye removal was applied to a synthetic effluent in batch mode. Adsorption experiments were performed by suspending sawdust in the effluent and analyzing the supernatant by spectrophotometry. The effectiveness of the treatment process was evaluated by measuring coloration. RESULTS AND DISCUSSION: Experimental results showed a significant potential for wood sawdust, especially coniferous sawdust, to remove cationic dyes from textile effluents. Adsorption kinetics was influenced by the initial dye concentration, nature and amount of sorbent as well as sorbent particle size. The adsorption followed a pseudo first-order kinetics. For both basic dyes, the Langmuir adsorption equation showed a better fit than the Freundlich equation. CONCLUSION: Filtration-adsorption using an inexpensive and readily available biosorbent provided an attractive alternative treatment for dye removal, and it does not generate any secondary pollution. Recommendations and Perspectives. Laboratory studies provide promising perspectives for the utilization of wood sawdust as renewable adsorbent for reducing pollution while enhancing the reuse of textile effluents. However, the treatment process needs to be applied to the other textile dye classes in order to be used on an industrial scale.     

Utilization of TiO2 deposited on glass plates for removal of metals from aqueous wastes

Glass plates coated with TiO2 were used in a photocatalytic process to collect mercury, lead, copper and cadmium from aqueous solutions containing individual metals and mixtures. Stripping voltammetry, verified to achieve 1-10 ppb detection limits, was used to show that individual metals at concentrations of 1000 to 5200 ppb were reduced to undetectable levels in 3 to 55 min. Capillary electrophoresis (CE) with 8-hydroxyquinoline-5-sulfonic acid as complexing agent was used when appropriate, since it could quantitate all four metals under study in one run although it was less sensitive. It was demonstrated that 100 mL solutions containing 10 ppm of each of the four metals could be treated with a 10 cm2 TiO2-coated plate to leave undetectable metal concentrations in one hour. Stripping voltammetry using carbon electrodes coated with mercury films was estimated to generate daily about 1.1 L of aqueous waste containing 0.1 ppm of each metal. The results indicate the feasibility of assembling an apparatus capable of treating the waste generated by stripping voltammetry to render the latter suitable for routine on-site analyses without environmental concern. Data were also obtained to show the effectiveness in treating silver containing solutions, indicating suitability of the photocatalytic process in treating photographic processing wastes.     

Mercury in sediment and fish communities of Lake Vänern, Sweden: recovery from contamination

The past effluents of mercury (Hg) into Lake V?nern were considerable. The consequences of, and recovery from these have been monitored through continuous measurements of mercury in sediment and fish. Mercury levels in lake sediments in the vicinity of the main source of mercury, a chloralkali plant on the northern shore, have only decreased by slightly more than a half since the mid-1970s, despite a radical decrease in effluents from the source, already during the 1960s. The mercury levels in pike (Esox lucius) have decreased to a similar extent during this time period. They are now about 30% higher in the worst affected parts of the lake compared to the least affected parts. Lower levels have been measured in perch (Perca fluviatilis) and salmonoid fish in the lake. Despite the increased presence of mercury in the sediment of Lake V?nern, the mercury levels in the fish of the lake are relatively low compared to fish in lakes situated in the same region, but not affected by any local mercury effluents. As calculated, the total fish biomass of L. V?nern holds less than 1000th of the amount of mercury contained in the upper, biologically active layers of the bottom sediment of the lake. This demonstrates the potential influence of various environmental factors and motivates continued monitoring of mercury levels in the lake in the future.     

The occurrence and removal of selected pharmaceutical compounds in a sewage treatment works utilising activated sludge treatment

Pharmaceutical substances have been detected in sewage effluents as well as receiving waters in many parts of the world. In this study, the occurrence and removal of a number of drug compounds were studied within a large sewage treatment plant in the south of England. Samples were processed using solid phase extraction and analysed using gas chromatography-mass spectrometry (GC-MS). The results demonstrate that ibuprofen, paracetamol, salbutamol and mefenamic acid were present in both the influent and effluent of the works while propranolol-HCl was not found above the limit of quantification in any sample. Elimination rates were circa 90% for each compound but several hundred nanograms per litre were still present in the final effluent.     

Sanitation of seawater effluent from seaweed processing plants using a photo-catalytic TiO2 oxidation

A fine porcelain open-cell photo-catalytic filter with titanium dioxide (TiO(2)) was evaluated for sterilization and sanitation of bio-polluted industrial water. In simulated seawater industrial effluent samples, the populations of Escherichia coli and Vibrio parahaemolyticus quickly decreased and reached non-detectable level within 10min. In seawater effluents from a seaweed processing plant, the bacterial populations in two samples quickly decreased by more than 10(3). In another two samples the decreases were slow and lowered by less than 10(2). Using fluorescence microscopy, it was indicated that the bacterial cells treated with photo-catalytic TiO(2) were damaged. In addition, the protein concentration in simulated seawater effluent slowly decreased using the photo-catalytic TiO(2) reaction; and reached similar concentrations as seawater near cultured seaweed beds. These results indicate that using a reactor with a TiO(2) photo-catalyst filter was effective for the sanitation of seawater effluents.     

城市生活污水及二级处理水中手足口病病毒及肠道病毒的赋存状态

手足口病是由多种肠道病毒引起的传染病,其主要病原体有EV71、CVA16及CVA10。为了研究污水处理厂的生活原污水及二级处理水中此类病毒的存活情况,实验利用手足口病3种主要病毒的通用引物对其进行分型检测,同时使用肠道病毒通用引物检测所有肠道病毒,并对常规水质指标进行分析。结果表明,原污水及二级处理水的手足口病病毒阳性率分别为83.3%与36.7%,而肠道病毒阳性率更高达100%及93.3%。说明生活污水中的肠道病毒可以稳定存在,且若未进行有效消毒处理,可能存在于二级处理水中。在3种手足口病主要病毒中,CVA10检出率最高,达45.0%,CVA16及EV71检出率分别为8.3%及10.0%。可推断,CVA10为实验阶段该地区主要的手足口病病毒。通过相关性分析,肠道病毒的存活与水质条件密切相关。     

A method for the analysis of organophosphorus pesticide residues in Mexican axolotl

A method based on matrix solid-phase dispersion (MSPD) was developed for quantitative extraction of three organophosphorus pesticides (OPPs) from the Mexican axolotl, Ambystoma mexicanum. The determination was carried out using high- performance liquid chromatography (HPLC) with diode array spectrophotometric UV detection (DAD). The MSPD extraction with octadecylsilyl (C18) sorbent combined with a silica gel clean-up and acetonitrile elution was optimised for chlorpyrifos, fenthion and methyl parathion. The method was validated, yielding recovery values higher than 90%. The precision, expressed as the relative standard deviation (RSD), was less than or equal to 6% in muscle samples at spiking levels of 10 and 5 ppm. Linearity was studied from 15 to 60 ppm for chlorpyrifos and fenthion, and from 7.5 to 30 ppm for methyl parathion. The limits of detection (LODs) were found to be less than or equal to 0.5 ppm_.This method was applied to the analysis of samples from a chlorpyrifos-exposed axolotl, demonstrating its use as an analytical tool for toxicological studies.     

Input/output balance of estrogenic active compounds in a major municipal sewage plant in Germany

24 h samples of untreated and treated wastewater were taken in parallel from a modern municipal sewage plant in southern Germany in March and June 1998. After solid phase extraction, total estrogenic activity was quantitatively measured with a miniaturized E-screen assay and the levels of nine estrogenic phenolic chemicals analyzed by HRGC/LRMS. 17Beta-estradiol equivalent concentrations (EEQ) were 58 and 70 ng/l in the influent and 6 ng/l in the effluent, indicating that the load of estrogenic activity of the wastewater was reduced by about 90% in the sewage plant. Less than 3% of the estrogenic activity was found in the sludge. 4-t-octylphenol, 4-nonylphenol, bisphenol A, 2-hydroxybiphenyl, and 4-chloro-3-methylphenol were detected in the untreated wastewater at levels from 0.13 to 3.6 microg/l. 4-t-octylphenol, 4-nonylphenol, and bisphenol A were present in the effluent at concentrations from 0.16 to 0.36 microg/l, 2-hydroxybiphenyl and 4-chloro-3-methylphenol were not detectable. The contribution of the quantified levels of phenolic xenoestrogens to total estrogenic activity in the sewage was 0.7-4.3%.     

Evaluation of municipal sewage treatment systems for pollutant removal efficiency by measuring levels of micropollutants

In order to evaluate the municipal sewage treatment systems used at Harbin municipal sewage treatment plant for their pollutant removal efficiency, raw sewage and effluent samples at different treatment stages from the sewage treatment systems were taken, priority pollutants (PPs) were identified and quantified using gas chromatography-mass spectrometry (GC-MS) and inductively coupled plasma-atomic emission spectrograph (ICP-AES). The test results indicated that there were one hundred and fifty species of organic pollutants identified in the raw sewage sample, and only ten species of PPs in all the sewage samples. The levels of dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), di-n-octyl phthalate (DnOP) in the sewage samples were 0.779-0.111 microg l(-1), 1.977-0.022 microg l(-1), 6.411-2.194 microg l(-1) and 7.152-2.953microg l(-1), respectively, and most of these phthalate esters (PAEs) were removed through anaerobic/aerobic (A/O) process; The levels of alachlor, acetochlor, atrazine were 0.074-0.021 microg l(-1), 0.160-0.096 microg l(-1) and 0.238-0.184 microg l(-1), respectively, and the total removal efficiency of atrazine was poorest through the sewage treatment systems. The levels of Cu, Cr, Se, Hg, Ni and Zn were 0.0030-0.2327 mg l(-1). It is therefore concluded from these results that the sewage treatment systems were efficient in removing most of the organic and inorganic compounds in this study, and so, the discharged effluent could cause little of the secondary pollution of the aquatic environment.     

Recent trends of biocides in pikes of the Lake Päijänne

Pikes were sampled in May 1980 from three areas of the Lake Päijänne, Finland and analyzed for their contents of total mercury, methyl mercury, hexachlorobenzene (HCB), DDE, PCB and chlorophenolic residues. An improved method for methyl mercury determination was applied and 82–84 % methylation of mercury in pikes regardless of area or biological variation was observed. Statistical analysis with previous results from the same areas gave a very significant decreasing trend of mercury levels at all three areas from 1970 to 1980. Future levels of mercury in fish to be consumed as food could be estimated from the trend regression. The very low levels of DDE and PCB showed some increasing trend when the influence of fat contents was eliminated by covariance analysis. General appearance of HCB at sub-ppb level was observed. Also pentachlorophenol occured at 10–70 ppb (fresh weight) levels at all areas, but the other chlorophenols were abundant only at Tiirinselkä which is most contaminated by pulp bleaching effluents.     

Evaluation of UV/TiO(2) and UV/ZnO photocatalytic systems coupled to a biological process for the treatment of bleaching pulp mill effluent

This paper presents an exploratory study of pulp mill bleaching effluent treatment by a biological-photocatalytic coupled system. A fungus, Trametes pubescens, immobilized on polyurethane foam was used to inoculate the biological pre-treatment system. The pretreated effluent was then exposed to a photocatalytic treatment in which two catalysts (TiO₂ and ZnO) and two supports (aluminum foil and Luffa cylindrica) were tested. Catalyst characterization was carried out by means of X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). Information about crystalline structure, chemical composition, morphology, homogeneity and distribution on the support surface area was obtained. The overall biological-photocatalytic coupled system achieved degradation of 96% of initial total organic carbon (TOC), 97% of 2-chlorophenol (2-CP), 90% of 2,4-dichlorophenol (2,4-CP) and 99% of 2,4,6-trichlorophenol (2,4,6-TCP). This approach of synergistic coupling of T. pubescens and a semiconductor photocatalyst appears to be a viable alternative for the treatment of these non-biodegradable effluents.     

Endocrine disrupting compounds in municipal and industrial wastewater treatment plants in Northern Greece

The occurrence and fate of endocrine disrupting compounds (EDCs) in a sewage treatment plant and two industrial wastewater treatment plants from textile and tannery factories were investigated. EDCs of interest are 4-nonylphenol, 4-octylphenol, their ethoxylate oligomers (mono- and di-ethoxylates of nonylphenol and octylphenol), bisphenol A, triclosan and steroid estrogens. Target compounds were determined in dissolved fraction, total suspended solids and sludge by employing solid phase extraction and ultrasonication followed by gas chromatography–mass spectrometry.Nonylphenols and oligomers with one or two ethoxy groups were the most abundant compounds in raw wastewater as well as in effluents from all the treatment stages of sewage treatment plant, followed by triclosan and bisphenol A. Steroids were found at very low concentrations. Almost all phenolic EDCs compounds were predominantly associated to suspended solids in influents whereas the dissolved fraction dominated the treated effluents. High removal rates, ranging from 86% to 99%, were observed throughout the whole treatment process. Biodegradation was the main removal pathway of EDCs. Tannery wastewaters exhibited high concentrations of nonylphenolic compounds. This type of wastewaters could pose a significant risk to the aquatic and terrestrial environment.     

Total mercury concentrations in an industrialized catchment,the Thur River basin (north-eastern France): geochemical background level and contamination factors

River bottom sediments and soils were collected from the industrialized Thur River basin (north-eastern France) to assess mercury contamination. The regional geochemical background level of total mercury was evaluated to calculate mercury contamination factors (Fc) in soils and river bottom sediments. Our estimate of the mean background mercury levels in river sediments and soils, not affected by human activities, was 232 ng x g(-1) (range: 27-406 ng x g(-1)). Sediments contaminated by the effluent from a chlor-alkali plant yielded the highest contamination factors (Fc=1784). Contamination factors of surficial soils within 1 km of the industrial site range from 6.3 to 43.6. This contamination is attributed to diffuse atmospheric deposition from this local plant. However, even upstream from this industrial area elevated contamination factors were recorded for river bottom sediments (Fc=3.2 to 26.4) and for one alluvial soil profile (Fc=10). This is possibly due to past pollution resulting from waste water discharges. Mercury contamination in the different horizons of alluvial soils is not correlated with soil organic carbon content, but may be the result of occasional accidental pollution arising from the introduction of contaminated suspended particulate matter by the Thur River during periods of flooding.     

How seasonality affects the flow of estrogens and their conjugates in one of Japan's most populous catchments

A detailed study of the free and conjugated estrogen load discharged by the eight major sewage treatment plants into the Yodo River basin, Japan was carried out. Sampling campaigns were focused on the winter and autumn seasons from 2005 to 2008 and the free estrogens estrone(E1), 17β-estradiol(E2), estriol(E3), 17α-ethynylestradiol(EE2) as well as their conjugated (sulfate and glucuronide) forms. For both sewage effluent and river water E2 and E1 concentrations were greatest during the winter period (December-March). This coincides with the period of lowest rainfall and lowest temperatures in Japan. E1 was the dominant estrogenic component in effluent (means of 10-50 ng/L) followed by E2 (means of 0.5-3 ng/L). The estrogen sulfate conjugates were found intermittently in the 0.5-1.7 ng/L concentration range in the sewage effluents. The greatest estrogen exposure was found to be in the Katsura River tributary which exceeded 1 ng/L E2-equivalents during the winter period.     

BOD5 measurements of water presenting inhibitory Cu2+. Implications in using of BOD to evaluate biodegradability of industrial wastewaters

In industrial effluents, the presence of an infinite number of possible mixtures of substances and the high variability of chemical conditions ask for an evaluation of biodegradability by a global and simple method. Biological oxygen demand after five days (BOD5) using synthetic wastewater was studied by two different ways: dilution and manometric methods. It can therefore be established that BOD5 obtained by adding manufactured inocula to the synthetic medium (effluent containing known and easily biodegradable substances) is close to the values obtained with inocula taken from the treated effluent of an urban and a rural purification plant. It was found that BOD5 measurement of effluents presenting factors affecting biodegradation, similar of those found in industrial effluents, is very questionable. The BOD is in this case influenced by the synergic and antagonist interactions between numerous and variable parameters like as pH, nature and concentration of inoculum, concentration of nutriments, amount and nature of assimilable substances, presence of toxicants, and presence of nitrification inhibitors, which are typical of real industrial wastewaters.     

Synthetic polycyclic musks in Hong Kong sewage sludge

Synthetic polycyclic musks [Cashmeran (DPMI), Celestolide (ADBI), Phantolide (AHMI), Traseolide (ATII), Tonalide (AHTN), and Galaxolide (HHCB)] were determined in dewatered sludge samples from 10 major sewage treatment plants in Hong Kong using primary treatment (PT), secondary treatment (SecT) or chemical-enhanced primary treatment (CEPT) methods. The concentrations of HHCB, AHTN, AHMI and ADBI ranged from below detection limits to 78.6mg/kg dry weight. HHCB and AHTN were the two predominant polycyclic musks in sludge samples, suggesting the extensive use of these two polycyclic musks in Hong Kong. Polycyclic musk levels in CEPT sludge were significantly higher than those in SecT and PT sludge, suggesting that CEPT sludge has a higher ability to retain polycyclic musks. Comparisons to global concentrations revealed that HHCB and AHTN concentrations detected in Hong Kong sludge ranked first and second respectively. However, the estimated levels of HHCB and AHTN in the discharged effluent from sewage treatment plants may pose low potential risks to aquatic organisms according to the threshold effect levels derived for fish. Nevertheless, the polycyclic musks released in sewage treatment plant effluents may bioconcentrate and bioaccumulate in the marine environment in Hong Kong. Therefore, monitoring studies in marine ecosystems, particularly on the two prevailing polycyclic musks, are necessary.