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.

     

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.     

Grazing rates of organic matter and living fungal biomass of decaying Spartina alterniflora by three species of salt-marsh invertebrates

 The pathway for the flow of salt-marsh grass production into marsh food-webs is still not well defined. We compared the abilities of three marsh macroinvertebrates [salt marsh periwinkles, Littoraria irrorata (Say) (=Littorina irrorata), salt-marsh coffee-bean snails, Melampus bidentatus (Say); and a talitrid amphipod, Uhlorchestia spartinophila Bounsfield and Heard] to access standing-dead leaves of smooth cordgrass (Spartina alterniflora Loisel). The invertebrates were incubated with naturally-decaying leaves, and the rates of removal of organic matter and living fungal biomass (ergosterol) were measured. The impact of invertebrate activity upon fungal growth rates was measured as rates of fungal-membrane synthesis (incorporation of radioacetate into ergosterol). The removal rates of organic leaf biomass per mg individual biomass were highest for amphipods (700 μg mg⁻¹ d⁻¹) and lowest for periwinkles (90 μg mg⁻¹ d⁻¹), but the relatively large biomass of the snails made their removal rates per individual greater than those of amphipods. Net removal of ergosterol by all three invertebrates was >50% for yellow-brown (early-decay) leaf blades. For fully-brown (advanced-decay) blades, >50% removal of ergosterol was found only for periwinkles; exposure to coffee-bean snails and amphipods resulted in a net ergosterol reduction of ≤20%. The lower net reduction of living fungal biomass by coffee-bean snails and amphipods may have been due to fungal-growth stimulation (2.3-fold stimulation in coffee-bean snails and 1.5-fold stimulation in amphipods). Grazing by periwinkles did not stimulate fungal growth, possibly because of its high intensity. Grazing by these three salt-marsh shredders may affect marsh-grass shoot-decay in different ways. Periwinkles may abbreviate the period of fungal production, and incorporate the decaying material relatively quickly into snail biomass and fecal-pellet rain to the sediments. Coffee-bean snails and amphipods may enhance and prolong fungal production, along with the formation of fecal-pellet rain. All three invertebrates fed preferentially on leaf blades rather than leaf sheaths, and feeding rates of gastropods were higher during the night than during the day. Received: 25 November 1998 / Accepted: 4 November 1999     

Transfer of Graphene CVD to Surface of Low Density Polyethylene (LDPE) and Poly(butylene adipate-co-terephthalate) (PBAT) Films: Effect on Biodegradation Process

Here, the influence of graphene as a coating on the biodegradation process for two different polymers is investigated, poly(butylene adipate-co-terephthalate) (PBAT) (biodegradable) and low-density polyethylene (LDPE) (non-biodegradable). Chemical vapor deposition graphene was transferred to the surface of two types of polymers using the Direct Dry Transfer technique. Polymer films, coated and uncoated with graphene, were buried in a maturated soil for up to 180 days. The films were analyzed before and after exposure to microorganisms in order to obtain information about the integrity of the graphene (Raman Spectroscopy), the biodegradation mechanism of the polymer (molecular weight and loss of weight), and surface changes of the films (atomic force microscopy and contact angle). The results prove that the graphene coating acted as a material to control the biodegradation process the PBAT underwent, while the LDPE covered by graphene only had changes in the surface properties of the film due to the accumulation of solid particles. Polymer films coated with graphene may allow the production of a material that can control the microbiological degradation, opening new possibilities in biodegradable polymer packaging. Regarding the possibility of graphene functionalization, the coating can also be selective for specific microorganisms attached to the surface.     

Vermicomposting as an advanced biological treatment for industrial waste from the leather industry

The leather industry (tanneries) generates high amounts of toxic wastes, including solid and liquid effluents that are rich in organic matter and mineral content. Vermicomposting was studied as an alternative method of treating the wastes from tanneries. Vermicompost was produced from the following tannery residues: tanned chips of wet-blue leather, sludge from a liquid residue treatment station, and a mixture of both. Five hundred earthworms (Eisenia fetida) were added to each barrel. During the following 135 days the following parameters were evaluated: pH, total organic carbon (TOC), organic matter (OM), cation exchange capacity (CEC), C:N ratio, and chromium content as Cr (III) and Cr (VI). The results for pH, TOC and OM contents showed decreases in their values during the composting process, whereas values for CEC and total nitrogen rose, indicating that the vermicompost reached maturity. For chromium, at 135 days, all values of Cr (VI) were below the detectable level. Therefore, the Cr (VI) content had probably been biologically transformed into Cr (III), confirming the use of this technique as an advanced biological treatment. The study reinforces the idea that vermicomposting could be introduced as an effective technology for the treatment of industrial tannery waste and the production of agricultural inputs.     

Mercury species accumulation and trophic transfer in biological systems using the Almadén mining district (Ciudad Real,Spain) as a case of study

The impact of mercury (Hg) pollution in the terrestrial environments and the terrestrial food chains including the impact on human food consumption is still greatly under-investigated. In particular, studies including Hg speciation and detoxification strategies in terrestrial animals are almost non-existing, but these are key information with important implications for human beings. Therefore, in this work, we report on Hg species (inorganic mercury, iHg, and monomethylmercury, MeHg) distribution among terrestrial animal tissues obtained from a real-world Hg exposure scenario (Almadén mining district, Spain). Thus, we studied Hg species (iHg and MeHg) and total selenium (Se) content in liver and kidney of red deer (Cervus elaphus; n?=?41) and wild boar (Sus scrofa; n?=?16). Similar mercury species distribution was found for both red deer and wild boar. Major differences were found between tissues; thus, in kidney, iHg was clearly the predominant species (more than 81 %), while in liver, the species distribution was less homogeneous with a percentage of MeHg up to 46 % in some cases. Therefore, Hg accumulation and MeHg transfer were evident in terrestrial ecosystems. The interaction between total Se and Hg species has been evaluated by tissue and by animal species. Similar relationships were found in kidney for both Hg species in red deer and wild boar. However, in liver, there were differences between animals. The possible underlying mechanisms are discussed.