Heavy metals in untreated/treated urban effluent and sludge from a biological wastewater treatment plant

Background, Aim and Scope

The presence of heavy metals in wastewater is one of the main causes of water and soil pollution. The aim of the present study was to investigate the removal of Cd, Cu, Pb, Hg, Mn, Cr and Zn in urban effluent by a biological wastewater treatment, as well as to quantify the levels of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sn, Tl, V and Zn in dewatering sludge from the Biological Wastewater Treatment Plant to Ribeirão Preto (RP-BWTP), Brazil.

Materials and Methods

Concentrations of Cd, Cr, Cu, Mn and Pb in wastewater and those of Ni in sludge were determined by atomic absorption spectrophotometry with graphite furnace atomization. Mercury concentrations in wastewater were measured by hydride generation atomic spectrophotometry, and Zn levels were determined by atomic absorption spectrophotometry using acetylene flame. In sludge, the levels of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Pb, Sn, Tl, V and Zn were determined by inductively coupled plasma-mass spectrometry.

Results

The percentages of removal efficiency (RE) were the following: Hg 61.5%, Cd 60.0%, Zn 44.9%, Cu 44.2%, PB 39.7%, Cr 16,5% and Mn 10.4%. In turn, the mean concentrations (mg/kg) of metals in dewatering sludge followed this increasing order: Tl (<0.03), Hg (0.31), Be (0.43), As (1.14), Cd (1.34), V (59.2), Pb (132.1), Sn (166.1), Cr (195.0), Mn (208.1), Ni (239.4), Cu (391.7), Zn (864.4) and Fe (20537).

Discussion

The relationship between metal levels in untreated wastewater, as well as the removal efficiency are in agreement with previous data from various investigators, It is important to note that metal removal efficiency is not only affected by metal ion species and concentration, but also by other conditions such as operating parameters, physical, chemical, and biological factors.

Conclusions

Metal values recorded for treated wastewater and sludge were within the maximum permitted levels established by the Environmental Sanitation Company (CETESB), São Paulo, Brazil.

Recommendations

There is an urgent need for the authorities who are responsible for legislation on sludge uses in agriculture of establishing safety levels for As, Be, Hg, Sn, Tl and V.

Perspectives

According to the current metal levels, RP-BWTP sludge might be used for agriculture purposes. However, for an environmentally safe use of sewage sludge, further studies including systematic monitoring are recommended. Annual metal concentrations and predicted variations of those elements in the sludge should be monitored.

     

Dioxin formation in pulp and paper mills of India

Samples of effluents, sludge, pulp, final products (paper) and soil were collected from the identified pulp and paper mills in India. The samples were analysed for 2,3,7,8-tetrachloro-dibenzo-p-dioxin (2,3,7,8-TCDD) and other dioxin congeners and precursors. Pulp and paper mills using chlorine for the bleaching process showed the presence of 2,3,7,8-TCDD in effluent samples. In the effluent and pulp samples from mills where chlorine dioxide was used as a bleaching agent, the 2,3,7,8-TCDD congener ranged from below the detection limit 0.05 to 0.12 ngL⁻¹/ngg⁻¹. The relative standard deviation of reproducibility and the percent recovery of 2,3,7,8-TCDD were 2.07 and 82.4% in pulp and 2.8 and 92% in effluent, respectively. The 1,3,6,8-TCDD was the only other major dioxin congener found in the treated and untreated effluent and sludge samples. However, dichlorobenzene, trichlorophenyl, and hexachlorobiphenyl were detected in all samples. The formation of dioxins can be minimised by replacing chlorine with chlorine dioxide in bleaching processes in pulp and paper mills.     

Influence of urbanization and tourist activities on the water quality of the Potrero de los Funes River (San Luis – Argentina)

A study of the water quality of the Potrero de los Funes River (San Luis – Argentina) was carried out in order to evaluate the possible effect of the anthropogenic activities on the river developed in the homonymous town. Samples were collected during the period March 2000–November 2005 at three selected sampling sites (RP₁, RP₂ and RP₃). Different physicochemical and bacteriological parameters (turbidity, pH, conductivity, suspended solids, alkalinity, potassium, sodium, calcium, magnesium, chlorides, nitrates, phosphates, sulphates, chemical oxygen demand (COD), 5-day biological oxygen demand (BOD₅), dissolved oxygen, total coliforms, Escherichia coli and total heterotrophic bacteria) were analysed according to the Standard Method for the Examination of Water and Wastewater. When comparing the values of total coliforms, E. coli, total heterotrophic bacteria, COD, BOD₅ and phosphates from the zone without anthropogenic influence (RP₁) and the urban zones (RP₂ and RP₃) an important variation in the parameters was observed. These results indicate that the urban activity produces a serious and negative effect on the water quality, thus constituting a sanitary risk and may have a major impact on the trophic status of the Potrero de los Funes dam. As case study, we report on the use of General Quality Index (GQI) to evaluate spatial and seasonal changes in the water quality of Potrero de los Funes River. Results revealed a significant degradation of the water quality at RP₂ and RP₃.     

Testing the use of juvenile Salmo trutta L. as biomonitors of heavy metal pollution in freshwater

Individual specimens of Salmo trutta were captured, from four sampling sites in Galician rivers (NW Spain) affected by different types of contamination: diffuse urban waste, run-off from an unrestored dump at a copper mine and waste from a fish farm. The ages of the captured trouts were established and only those belonging to the 1+ age class were selected for study. The liver and kidney were removed from each fish and analysed to determine the tissue concentrations of Cu, Fe and Zn. The results obtained showed that: (i) the use of 1+ individuals allowed differentiation of contamination scenarios on the basis of the tissue concentrations of metal; (ii) the use of 1+ individuals allowed standardization of the time of exposure, which was sufficiently long for differential uptake to have taken place; (iii) liver tissue provided the best results as, less effort was required than for processing kidney tissue, and significant differences between sampling sites were detected because the intrapopulational variability in metal levels was lower than for kidney, and (iv) the levels of elements detected were not affected by basal tissue concentrations or residual concentrations due to past contamination, which older trouts may have been exposed to. In addition, the use of 1+ trout may provide better results in annual environmental sampling surveys.     

Diel cycles of arsenic speciation due to photooxidation in acid mine drainage from the Iberian Pyrite Belt (Sw Spain)

Twenty four hours diel cycles of arsenic speciation in Acid Mine Drainage (AMD) due to photooxidation have been reported for the first time. AMD samples were taken during 48 h (31st March and 1st April, 2005) at 6 h intervals from the effluent of a massive abandoned polymetallic sulphide mine of the Iberian Pyrite Belt (Sw Spain). Samples were preserved in situ using cationic exchange prior to analysis by coupled high performance liquid chromatography, hydride generation and atomic fluorescence spectrometry (HPLC-HG-AFS) for arsenic speciation. The results indicated the presence of inorganic arsenic species with daily means of 262mugl(-1) for As(V) and 107 microg l(-1) for As(III). No marked diel trend was observed for As(V). However, a marked diel trend was observed for As(III) in the two studied days, with maximum concentrations during nighttime (141-143 microg l(-1)) and minimum concentrations at daytime (72-77 microg l(-1)). This difference in concentration during daytime and nighttime is ca. 100%. A similar diel cycle was observed for iron. An explanation for the arsenic diel cycles observed is the light induced photooxidation of As(III) and the elimination of As(V) due to its adsorption onto Fe precipitates during the daytime. Furthermore, the diel changes in arsenic speciation emphasize the importance of designing suitable sampling strategies in AMD systems.     

A field trial for an ex-situ bioremediation of a drilling mud-polluted site

The remediation of drilling mud-polluted sites in the Southeast of Mexico is a top priority for Mexican oil industry. The objective of this work was to find a technology to remediate these sites. A field trial was performed by composting in biopiles, where four 1ton soil-biopiles were established, one treatment in triplicate and one unamended biopile. Amended biopiles were added with nutrients to get a C/N/P ratio of 100/3/0.5 plus a bulking agent (straw) at a soil/straw ratio of 97/3. Moisture content was maintained around 30-35%. Results showed that, after 180 d, total petroleum hydrocarbon (TPH) concentrations decreased from 99300+/-23000mgTPHkg(-1) soil to 5500+/-770mgTPHkg(-1) for amended biopiles and to 22900+/-7800mgTPHkg(-1) for unamended biopile. An undisturbed soil control showed no change in TPH concentrations. Gas chromatographic analysis showed residual alkyl dibenzothiophene type compounds. Highest bacterial counts were observed during the first 30 d which correlated with highest TPH removal, whereas fungal count increased at the end of the experimentation period. Results suggested an important role of the straw, nutrient addition and water content in stimulating aerobic microbial activity and thus hydrocarbon removal. This finding opens an opportunity to remediate old polluted sites with recalcitrant and high TPH concentration.     

Oxidation of trichloroethene over metal oxide catalysts: kinetic studies and correlation with adsorption properties

The performance of bulk chromium oxide is compared with that of a Mn commercial catalyst for the deep oxidation of trichloroethene (1000-2500ppmv, 55h(-1) space velocity) in air, in dry and wet (20000ppm of H(2)O) conditions, in terms of activity, selectivity and stability. Chromium oxide was found to be more active (on a catalyst weight basis), however its activity decreases continuously with time on stream. The presence of water increases its stability, the Mn catalyst showing the opposite behaviour. The effect of water on the Cr catalyst can be explained according to the Deacon equilibrium, as the presence of water tends to decrease the Cl(2) concentration, assumed to be responsible of the catalyst deactivation. Regarding to the selectivity, the Mn catalyst yields C(2)Cl(4), CCl(4) and CHCl(3) as organochlorinated by-products, whereas chromium oxide produces only trace amounts of CCl(4). Simple power-law kinetics expressions (first-order for Mn and zero-order for Cr) provide fairly good fits for the evolution of the conversion with the temperature. Furthermore, the kinetic behaviour of chromium oxide can be represented with a Langmuir-Hinshelwood model taking into account the chlorine inhibitory effect.     

Antimony distribution and mobility in topsoils and plants (Cytisus striatus, Cistus ladanifer and Dittrichia viscosa) from polluted Sb-mining areas in Extremadura (Spain)

A study about topsoil antimony distribution and mobility from the soils to the biomass has been afforded in three abandoned Sb mining areas located at Extremadura. Physico-chemical characteristics of the soils and total antimony levels were measured in soils and autochthonous plant species (Cytisus striatus, Cistus ladanifer and Dittrichia viscosa). Comparison with corresponding values in reference areas isolated from the mining activities is discussed. Antimony mobility in the soils was estimated by measuring the water extractable fraction; low results were obtained for the three soil areas, with no statistical differences. Plant ability to accumulate antimony was estimated by use of plant accumulation coefficients (PAC). Seasonal (spring vs. autumn) effects on the antimony content in the plant species. Cytisus striatus from Mari Rosa mine presented antimony excluder characteristics, whereas Dittrichia viscosa specimens growing in San Antonio mine showed a significant antimony bioaccumulation.     

Bioaccumulation of lead, mercury, and cadmium in the greater white-toothed shrew, Crocidura russula, from the Ebro Delta (NE Spain): sex- and age-dependent variation

We quantified bioaccumulation of lead, mercury, and cadmium in bones from 105 greater white-toothed shrews (Crocidura russula) collected at the Ebro Delta, a polluted area, and the Medas Islands, a control site. Lead and mercury levels varied with site, age, and sex, although statistical significances depended on each factor. Globally, shrews from the polluted area exhibited significantly higher concentrations of Pb and Hg. Increment of Pb with age was particularly remarkable in wetland animals and was interpreted in relation to human activities, namely hunting. Unlike males, females from the Ebro Delta maintained low Hg levels, which were associated with gestation and lactation. Cadmium levels did not differ between sites, sexes, or ages. This study provides the first data on heavy metals in mammals from this wetland and suggests that C. russula is a good bioindicator of metal pollution. We concluded that sex and age may represent an important source of variation in the bioaccumulation of these metals in wild populations.