Untreated Industrial Wastewater Research Articles

Tracing polar benzene- and naphthalenesulfonates in untreated industrial effluents and water treatment works by ion-pair chromatography-fluorescence and electrospray-mass spectrometry

This paper presents a protocol for the determination of a class of polar, ionic and highly water-soluble organic pollutants: benzene- and naphthalenesulfonic acids, compounds widely used in chemical, pharmaceutical, tannery, paper and textile industries. This protocol involves the use of a solid-phase extraction (SPE) followed by ion-pair chromatography-electrospray-mass spectrometry (IPC-ESI-MS). In this work two polymeric solid-phase extraction cartridges (Isolute ENV+ and Lichrolut EN) were compared, with the more effective being Isolute ENV+ sorbent. Recoveries and breakthrough volumes were calculated by loading volumes of 150, 200 and 300 ml of spiked ground water through the SPE columns. To enhance the effectiveness of the methodology, 1 ml of water containing 5 mM TEA was added before eluting with methanol. Average recoveries ranging from 70 to 100% were obtained for a variety of 13 analytes (only two naphthalenesulfonate compounds had recoveries below 50%.). Determination of benzene- and naphthalenesulfonates was accomplished by ion-pair chromatography-fluorescence detection (IPC-FLD). The ESI-MS parameters were optimized to achieve maximum sensitivity. [M–H] − ion was the base peak using low energies (fragmentor voltage: 80 V). Significant fragmentation of the quasi-molecular [M–H] − ion occurs at higher fragmentor voltages, leading to [M–SO 2H] −, [M–SO 3H] − and [SO 3] − as diagnostic ions, but with some sensitivity losses (more than two orders of magnitude when 150 V are applied as fragmentor voltage). Collision-induced dissociation (CID) of the parent ions for the benzene- and naphthalenesulfonates studied gave the [SO 3] − fragment ion common to sulfonated compounds, it has been shown to be characteristic of aromatic sulfonated compounds and could be used as a diagnostic tool to indicate the presence of these compounds. Limits of detection (signal-to-noise ratio = 3) ranging from 0.03 pg to 0.05 ng, were achieved when 150 ml of ground water were processed and quantified by IPC-FLD. In IPC-ESI-MS, time-scheduled SIM mode with post-column addition of 0.2 m min −1 of methanol was used. LODs range from 0.6 pg to 0.13 ng. In summary, with the development of a methodology based on SPE followed by IPC-ESI-MS, good sensitivity, structural information and unequivocal identification can be achieved. This protocol was applied to the analysis of surface waters, untreated industrial waste waters and wastewater treatment works effluents and influents. In the case of tannery effluent samples, isomers of naphthalenesulfonic acid were found as major pollutants in concentrations up to 0.8 and 1.0 mg l −1, for 1-naphthalenesulfonate and 2-naphthalenesulfonate, respectively. The main contaminants in wastewater treatment work samples were 2,6-naphthalenedisulfonate, 1-hydroxy-3,6-naphthalenedisulfonate, 3-nitrobenzenesulfonate, 1-naphthalenesulfonate and 2-naphthalenesulfonate, with levels of ug/l.

Dilution effects on the quality of untreated wastewater used for irrigation along the USA-Mexico border

The Juarez Valley, located along the USA-Mexico border, currently relies on untreated municipal and industrial wastewater from nearby Ciudad Juarez (est. pop. 1.6 million) which has been diluted with water diverted from the Rio Bravo (Rio Grande), and groundwater from underlying aquifers, to irrigate 18000 hectares of crops. The results indicate that dilution does very little to reduce the risks associated with the use of untreated wastewater for irrigation as faecal coliforms levels remained high (> 10 7 cfu/100 ml). Concentrations of heavy metals were low in the raw wastewater and in the mixed waters. However, the practice of diluting raw wastewater seriously degrades significant volumes of high quality waters from the Rio Bravo and from the underlying aquifer, and thus is not an optimal use of the limited high-quality water available to this semi-arid region.

Identification of Polar, Ionic, and Highly Water Soluble Organic Pollutants in Untreated Industrial Wastewaters

This paper presents a generic protocol for the determination of polar, ionic, and highly water soluble organic pollutants on untreated industrial wastewaters involving the use of two different solid-phase extraction (SPE) methodologies followed by liquid chromatography-mass spectrometry (LC-MS). Untreated industrial wastewaters might contain natural and synthetic dissolved organic compounds with total organic carbon (TOC) values varying between 100 and 3000 mg/L. All polar, ionic and highly water soluble compounds comprising more than 95% of the organic content and with major contribution to the total toxicity of the sample cannot be analyzed by conventional gas chromatography-mass spectrometry (GC-MS), and LC-MS is a good alternative. In this work two extraction procedures were used to obtain fractionated extracts of the nonionic polar compounds: a polymeric Isolute ENV + SPE cartridge for the preconcentration of anionic analytes and a sequential solid-phase extraction (SSPE) method percolating the samples first in octadecylsilica cartridge in series with the polymeric Lichrolut EN cartridge. Average recoveries ranging from 72% to 103% were obtained for a variety of 23 different analytes. Determination of nonionic pollutants was accomplished by reverse-phase liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS), while anionic compounds were analyzed by ion pair chromatography-electrospray-mass spectrometry (IP-ESI-MS) and LC-ESI-MS. Thismore » protocol was applied to a pilot survey of textile and tannery wastewaters leading to the identification and quantification of 33 organic pollutants.« less

Chemical forms and sorption of copper and zinc in soils of central Chile

Soil samples from a field irrigated with untreated industrial and municipal wastewater for several decades and from a field not receiving wastewater (control) were analyzed for total copper (Cu) and zinc (Zn) and for the amount of these elements removed in sequential extractions with MgCl2, NaOAc, NH2OH#lbHCl, 6H2O2‐HNO3‐NH4OAc, and HNO3‐HF‐HCl. Organically‐bound Cu forms predominated in the wastewater‐affected soil while in the control soil both residual and organic forms yielded the same proportion of Cu. Distribution of Zn was different in the diverse fractions, and in the polluted soil the reducible and the residual forms predominated while in the control soil the residual form accounted for the highest proportion of recovered Zn. Sequential extraction of Cu from a copper sulfate‐treated soil incubated for 32 days at constant temperature resulted in the same proportional distribution of Cu forms in the polluted soil. In the control soil the oxidizable form decreased and the residual one increased noticeably. The two‐surface Langmuir adsorption model was used to adjust data and to interpret Cu and Zn adsorption by soils excepting Cu sorption by the polluted soil, where the one‐surface model was applied.

Simultaneous determination of 3,4-dimethoxybenzaldehyde and 3,4-dimethoxyphenylacetone in industrial waste waters by high-performance liquid chromatography-diode array detection

The environmental pollutants 3,4-dimethoxybenzaldehyde (DMB) and 3,4-dimethoxyphenylacetone (DMPA) were separated and quantitatively determined in treated and untreated industrial waste waters on a porous graphitized carbon column using HPLC with diode array detection (DAD). It was established that the detector response is linear in a wide range of injected quantities for both pollutants, and the logarithm of the capacity factor depends linearly on the concentration of acetonitrile in the eluent. The relative standard deviation of the retention time, peak height and peak area was lower than 1% in the normal and lower than 3% in the lowest concentration range. Peak purity tests indicated that the method separates well DMB and DMPA from other impurities present in the waste waters. Both aerobic and anaerobic treatments markedly decreased the concentration of DMB and DMPA in industrial waters and HPLC combined with DAD proved to be an adequate analytical procedure to follow such changes.

Baseline studies of coastal pollution by heavy metals, oil and PAHs in Montevideo

Baseline studies of coastal pollution by heavy metals, oil and PAHs in Montevideo

Water quality changes of the river Meuse assessed by chironomid pupal exuviae

The chironomid fauna of the river Meuse in Belgium and The Netherlands was studied in order to determine spatial water quality variations. Because the river Meuse serves as a source for drinking water production for about five million people in Belgium and The Netherlands, water quality is an essential factor to be studied. From 1984 till 1989 pupal exuviae were collected. Water quality was assessed by several indices and autecological information of the various taxa. With regard to pollution the general trend through the years was the same. The most upstream sampling site, in the Belgian Ardennes, was relatively unpolluted. As a result of untreated industrial and municipal wastewater discharges in the Liege region, water quality deteriorated dramatically at the Dutch border. At the most downstream sampling site, near the river mouth, a slight recovery was observed. Apart from organic and inorganic pollution other environmental factors such as flow velocity and the nature of the riverbed, also play a significant role in the occurrence of the organisms. It is concluded that protective measures need to be taken to restore the affected river ecosystem.

Land Application of Untreated Industrial Waste Water

AbstractExcessive pretreatment of waste water prior to land application unduly increases the cost and energy requirement of land treatment systems. This study was conducted to determine if untreated industrial waste water can be applied to soil without adversely affecting crop growth and soil properties or posing a ground‐water pollution hazard.Untreated (UW) and treated (TW) waste water were diverted from the treatment plant at a fiberboard mill and spray‐irrigated on fescue‐grass (Festuca arundinacea Schreb) on Cecil soil (clayey kaolinitic, thermic Typic Hapludult) at 1.4 cm/week. After 2 years the treatments were changed to 1.5, 2.0, and 3.0 cm UW/week and continued for 2 more years.Grass yields with UW and TW were equal to or greater than yields with inorganic fertilizer and no irrigation (control treatment). Recovery of waste‐water‐applied N via crop harvest ranged from 20 to 30%. Analysis of washed and unwashed grass samples showed that increased Mn concentrations were due to waste‐water solids adhering to the sample, rather than to increased Mn uptake. Concentrations of Ni, Pb, and Cr of unwashed samples were increased slightly but were far below concentrations toxic to livestock.Soil nitrate concentrations resulting from UW applications were generally not significantly different from concentration in the control treatment except when UW contained appreciable quantities of inorganic N. There was evidence that denitrification was a significant N sink.Waste‐water irrigation increased concentrations of soil P, K, and Ca and increased soil pH to 7.4–7.8. Sodium accumulated in the subsoil to an exchangeable‐Na percentage of 10.Results of the study showed that extensive pretreatment was not necessary prior to irrigation with the waste water.

Heavy metals in sediments from the Athens sewage outfall area

Sediments in the upper Saronikos Gulf have been contaminated by heavy metals from the discharge of untreated industrial and domestic wastewater from the area around Athens. Neutron activation analysis indicates concentrations of antimony, arsenic, chromium, gold, mercury, silver and zinc are 8–200 times greater than in the surrounding uncontaminated sediments. The bottom area affected by increased metal concentrations is at least 13 km 2 and indicates a nearly radial dispersal pattern from the main outfall with higher concentrations extending to the southeast and southwest.

Assessment of nutrients and metals in sediments of Ogba river, Southern Nigeria

This study assesses the concentrations of nutrients and metals in river bed sediments of Ogba River, a fourth-order river in Southern Nigeria. Most rivers in this region are exposed to untreated industrial and domestic wastewater discharge, including atmospheric deposition from crude oil exploration activities. River bed sediment samples were collected from four sites located downstream of an urban sewage discharge and agro-allied industry wastewater release point. The results showed statistically significant differences in sediment particle size distribution, nutrient and metal concentrations across the sites. The sediment particle size distribution was dominated by sand (92%), with mean pH range of between 5.1 and 6.0. Concentrations of metals and nutrients were highest in sediments of Site 2 located in close proximity to refuse dump sites and arable land use. Total organic carbon (TOC) and nitrate (NO3--N) were negatively correlated with sand but positively related to clay (P<0.01). No significant relationship was found between metals except for Ni and cadmium (Cd), and Fe and Ni. In addition, no significant relationship was found between TOC and metals (Fe, Zn, Cu, Cd, Pb and Ni), suggesting that in this fluvial system TOC may not be effective in the complexation of metals.Key Words: Sediment, metals, nutrients, freshwater, Nigeria