Distribution of extractable fractions of heavy metals in sludge during the wastewater treatment process

Sludge samples were collected from different treatment steps of Gaobeidian wastewater treatment plant (WWTP) of Beijing City, PR China, to investigate the distributions of total and chemical fractions of Fe, Mn, Ni, Cu, Zn, Cr, Pb, and Mo in different sludges. The highest total concentrations were found for Fe, Mn, Pb, and Mo in digested sludge (DS), Ni and Cr in thickened sludge (TS), Zn in dewatering sludge (DWS), and Cu in active sludge (AS). The lowest concentrations were observed in AS, except for Cu in TS. Significant differences of total metal concentration were observed between AS and TS (or DS), suggesting that sludge thickening and digesting treatments significantly influenced the total metal concentrations. Fe, Cu, Ni, Cr, Mo, and Pb distributed principally in the residual fraction in all sludges, while Zn and Mn presented in a highly available fraction. For same metal in different sludges, the portion of easily mobile fraction decreased significantly along the wastewater treatment process, and metals in AS presented in the highest available fraction. Organic matter contents, TN, and TP of sludges exhibited a significant positive correlation with the concentrations of exchangeable and reducible fraction of Pb, Mo, Cr, Cu, and Fe, while sludge pH demonstrated significant negative correlations with the concentrations of these metals.     

Distribution of heavy metals in Lakes Doirani and Kerkini, Northern Greece

The distribution of heavy metals in two lakes of high ecological significance, Doirani and Kerkini, located in Northern Greece was studied. Eight metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) were determined in water, total suspended solids, fine and coarse sediments. Moreover, the modified BCR fractionation scheme was employed in sediments and suspended solids to determine soluble, oxidisable, reducible and residual fractions of metals. The Lake Doirani presents higher metal concentrations in aqueous phase than Lake Kerkini; Cd, Cu, Ni, Pb and Zn are above the chronic freshwater quality criteria for aquatic life. In both lakes, Fe and Mn are the most abundant elements in total suspended solids whereas Cd the less abundant. The Lake Kerkini exhibits higher concentrations of all the examined metals in sediments comparing to the Lake Doirani, however the concentrations are lower than the sediment quality guidelines. Cd in sediments is mainly in soluble fraction, Pb and Cu exhibit significant oxidisable fractions whereas, Cr and Fe associated mainly with residual fraction.     

Total concentrations and speciation of heavy metals in municipal sludge from Changsha, Zhuzhou and Xiangtan in middle-south region of China

The presence of heavy metals in municipal sludge restricts its use for agricultural purposes. In this paper, the bioavailability and eco-toxicity of heavy metals in municipal sludge was evaluated, taking into consideration both the speciation of metals and the local environmental characteristics. The dewatered municipal sludge samples were collected from five sewage plants in Changsha, Zhuzhou and Xiangtan respectively, which are representative cities with characteristics of the middle-south region of China. Some agricultural significant parameters and total metal concentrations in the sludge were determined and the metal speciation was studied by using BCR sequential extraction procedure. It was found experimentally that in general the municipal sludge collected from the five sewage plants was rich in organics, N and P. Except that the sludge from Xia Wan Sewage Treatment Plant showed higher concentrations of heavy metals, the sludge from other plants all showed a low total content of heavy metals with only Cd slightly exceeding the permitted values of the national application standard of acid soil in China (GB18918-2002). The sequential extraction results showed that Cu and Zn were principally distributed in the oxidizable fraction, which meant a high potential toxicity, but the bioavailability of Zn might be overestimated to the soil of Hunan. Pb was mainly in the residual fraction. The distribution of Cd showed no obvious characteristics.     

Effect of metal spiking on different chemical pools and chemically extractable fractions of heavy metals in sewage sludge

A laboratory experiment was conducted to study the effect of metal spiking and incubation on some properties and sequentially extractable chemical pools of some heavy metals (F1, two extractions with 0.1 M Sr(NO3)2; F2, one extraction with 1 M NaOAc (pH 5.0); F3, three extractions with 5% NaOCl (pH 8.5) at 90-95 degrees C; F4, three extractions with 0.2 M oxalic acid + 0.2 M ammonium oxalate + 0.1 M ascorbic acid (pH 3.0); and F5, dissolution of sample residue in HF-HClO4 (residual fraction,) and also 1 M CaCl2 and 0.005 M DTPA extractable heavy metals in sewage sludge. Metal spiking and incubation decreased pH and easily oxidizable organic C content of sludge but increased electrical conductivity. Metal spiking and incubation increased F1 fraction of all heavy metals, F2 fraction of Ni, Pb, Cu, and Cd, F3 fraction of Pb, Cu, and Cd, F4 or reducible fraction of Ni, Cu, and Cd and residual fraction of Zn and Pb, but decreased F2 fraction of Zn, F3 of Zn and Ni, F4 fraction of Zn and F5 fraction of Ni, Cu, and Cd. Metal spiking and incubation increased 1 M CaCl2 and 0.005 M DTPA extractable amounts of all heavy metals in sludge except for 0.005 M DTPA extractable Zn, which registered only very marginal decrease.     

Use of sequential leaching, mineralogy, morphology and multivariate statistical technique for quantifying metal pollution in highly polluted aquatic sediments--a case study: Brahmani and Nandira Rivers, India

The particle size distribution, geochemical composition and sequential leaching of metals (Fe, Mn, Ni, Cu, Co, Cr, Pb, Zn and Cd) are carried out in core sediments (<88 microm) from the Brahmani and Nandira Rivers, India. To confirm the contamination of downstream sediments by fly ash, mineralogical and morphological characterizations were carried out. High environmental risk of Co, Pb and Ni is due to their higher availability in exchangeable fraction. The metals like Zn, Cu and Mn represent an appreciable portion in the carbonate phase. Metals such as Zn, Pb, Cd, Co and Ni are associated with reducible phase may be due to adsorption. The organic bound Cu, Zn, and Pb seem to be second dominant fraction among non-lithogenous in Nandira sediments. Factor analysis data reveals that textural parameters, Fe-Mn oxy/hydroxides, organic precipitation and coal fly ash disposals, are individually responsible for the enrichment of heavy metals. The relationships among the stations are highlighted by cluster analysis to identify the contamination levels.     

Potential use of treated wastewater and sludge in the agricultural sector of the Gaza Strip

Twelve elements (Ag, Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were analyzed in 120 composite samples of influent and effluent wastewater; the results revealed that domestic wastewater influent contains considerable amounts of heavy metals and the partially functional treatment plants of Gaza are able to remove 40–70% of most metals during the treatment process. Heavy metals in 31 industrial wastewater effluents are within the ranges of international standards. All industries of Gaza are light; although they have no treatment facilities, their effluents are being discharged to municipal sewerage system and the existing treatment plants are capable of absorbing the industrial effluents with no significant impact on treatment bioprocesses.Thirty parameters were determined in 35 sludge samples: P, AOX, C, S, CaCO₃, Mg, Ca, Na, K, Li, Cu, Zn, Ni, Pb, Mn, Fe, Cr, Co, Cd, As, Hg, Ti, Se, Br, Rb, Th, Sr, Y, U, and Zr. Although there are no treatment facilities for sludge within the treatment plants, the results indicated that sludge in general is clean of heavy metals. Only Zinc and AOX showed anomalous concentrations; more than 85% of sludge samples showed that averages of zinc and AOX are 2,000 mg/kg and 550 mg Cl/kg, respectively, which exceed the standards of all industrial countries for sludge to be used in land application.     

Phytotoxicity and heavy metals speciation of stabilised sewage sludges

The presence of heavy metals in the sludges produced in wastewater treatment restricts plants growth and hence their use for agricultural purposes. This study looks at different types of sludges (aerobic, anaerobic, unstabilised and sludge from a waste stabilisation pond) and compares the distribution of the heavy metals that they contain according to the treatment that they have undergone. The sewage sludges were subjected to chemical characterisation and phytotoxicity testing (in absence of substrate) to provide a preliminary assessment of their suitability for land application. In addition, the total quantity of metals (Cd, Cr, Cu, Ca, K, Fe, Mg, Ni, Na, Pb and Zn) was determined. The Community Bureau of Reference (BCR) method for heavy metal speciation was followed. It was confirmed that the total concentration of heavy metals did not exceed the limits set out by European legislation and that the stabilisation treatment undergone by the sludges strongly influenced the heavy metal distribution and the phases to which they were associated. The sludge extracts did not exert any significant adverse effect on the relative seed germination (RSG) of barley (Hordeum vulgare L.) or cress (Lepidium sativum L.), although the reduction in germination index (GI) indicates that some characteristics existed did have an adverse effect on root growth.     

Concentration and speciation of heavy metals in six different sewage sludge-composts

This study presents the concentrations and speciation of heavy metals (HMs) in six different composts of sewage sludges deriving from two wastewater treatment plants in China. After 56 days of sludge composting with rice straw at a low C/N ratio (13:1), cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) were enriched in sludge composts, exhibiting concentrations that varied from 0.75 to 2.0, 416 to 458, 66 to 168 and 1356 to 1750mgkg(-1) dry weight (d.w.), respectively. The concentrations increased by 12-60% for Cd, 8-17% for Cu, 15-43% for Pb and 14-44% for Zn compared to those in sewage sludges. The total concentrations of individual or total elements in the final composts exceeded the maximum permissible limits proposed for compost or fertilizer. In all the final composts, more than 70% of total Cu was associated with organic matter-bound fraction, while Zn was mainly concentrated in exchangeable and Fe-Mn oxide-bound fractions which implied the high mobility and bioavailability. Continuously aerated composting treatment exhibited better compost quality and lower potential toxicity of HMs, whereas inoculant with microorganism and enzyme spiked during composting had no obvious advantage on humification of organic matter and on reducing HM mobility and bioavailability.     

Characteristics and accumulation of heavy metals in sediments originated from an electroplating plant

Heavy metals in river water and sediments originated from an electroplating plant in Jiangsu Province of China were studied and analyzed for their environmental impact. The results indicated that the wastewater from the plant degraded the quality of the aquatic environment downstream from the plant. In surface water, considerable concentrations of Cu, Ni, Zn, Mn and Cr were present at the sites near the plant. Unsafe levels of Cu were observed at all sites, and unsafe levels of Ni, Zn, and Cr were present at some sites. Significant accumulation of Ni, Cu, Zn and Cr was identified, and heavy metal longitudinal distribution in sediments was similar to that in water. The contents of Ni, Cu and Cr at all sites and Zn at some sites were likely to result in harmful effects on the environment. The risks posed by Ni, Cu, Zn and Cr in water and sediments decreased with increasing downstream distance. Moreover, a modified sequential extraction procedure was employed to determine exchangeable, carbonate-bound, iron-manganese oxide bound, organic matter bound and residual fractions of metals in sediments. The results showed that Ni was distributed in every fraction except for iron-manganese oxide bound, significant Mn exhibited in exchangeable fractions, and high percentage of Cu was in the organic matter and residual fractions. Residual fraction was the dominant fractions for Pb and Zn. According to RACs, Ni and Mn posed a high risk to the environment, Zn exhibited medium to high risk, Cu had low to high risk, and Pb possessed a low to medium risk.     

Speciation of heavy metals in untreated sewage sludge by using microwave assisted sequential extraction procedure

A fast microwave assisted extraction procedure was developed and optimized for their eventual exploitation in the three-stage sequential extraction procedure proposed by modified BCR protocol (the community Bureau of Reference now the European Union "Measurement and Testing Programme"). The effects of the microwave treatment on the extraction of Cd, Cr, Cu, Ni, Pb and Zn from untreated sewage sludge collected from Hyderabad city (Pakistan) were compared with those obtained from sequential BCR extraction procedure. In sequential BCR method, each extraction step takes 16 h, where as with the use of compromised microwave conditions, extraction steps could be completed in about 120 s, for each step, respectively. Extractable Cd, Cr, Pb and Ni obtained by both comparable methodologies were measured by electrothermal atomic absorption spectrometry (ETAAS), while for Cu and Zn flame atomic absorption spectrometry (FAAS) was used. The validations of both extraction techniques were compared by the analysis of certified reference material of soil amended with sewage sludge (BCR 483). The results of the partitioning study of untreated waste water sewage sludge, indicate that more easily mobilized forms (step 1) were predominant for Cd, Ni and Zn (28.3, 28.4 and 43.7%), in contrast, the largest amount of Cd and Pb (66.4 and 72.8%) was associated with the iron/manganese oxide while Cr and Ni (71.2 and 38.7%) in organic matter/sulphide fractions. The overall metal recoveries in steps 1-3 (excluding residual step) were 95.3-104% of those obtained with the sequential BCR protocol. The accuracy of the proposed microwave extraction method (expressed as %R.S.D.) was lower than 10% for all metals.     

Impact of thermal treatment on metal in sewage sludge from the Psittalias wastewater treatment plant, Athens, Greece

This paper describes a laboratory study that examined the effect of thermal treatment at four different temperatures on the behavior of heavy metals in the anaerobically treated primary sludge from the Psittalias wastewater treatment plant. The sewage sludge was found to contain significant amounts of heavy metals (Cr, Cu, Fe, Ni, Pb and Zn). The metal form distribution in the sludge samples which was determining by the application of a sequential extraction procedure revealed that a significant portion of metals was embodied in the organic and reducible fractions. Treatment at 105, 250, 650 and 900 degrees C demonstrated significant conversions of the metals to a less mobile form as well as removal by vaporization. By applying sequential analysis, it was found that most of the metals were removed from the initial mobile phases to more stable ones. Also, significant amounts were transformed to the gaseous phase.     

Assessment of the metal pollution, potential toxicity and speciation of sediment from Algeciras Bay (South of Spain) using chemometric tools

A study to determine total and mobile heavy metals concentrations in sediments from Algeciras Bay was performed and pollution hotspots were identified. The effects on aquatic organisms were established using sediment quality guidelines (SQGs). Ni and Cr exceeded the effect range medium and low levels, respectively, around industrial area. Potential toxicity of metals was determined by diethylenetriaminepenta-acetic acid (DTPA) extractions and low alert levels of Co, Cu, Zn, Cd, Ni and Pb were exceeded at most sampling sites. Three pollution indicators were used showing significant values for As, Ni, Cr, Pb and Cd. Sediment speciation using the sequential extraction BCR procedure was carried out, being Cd, Zn, Pb and As the most available metals. Principal component, cluster and ANOVA analyses were performed in order to assess the sources of metals and the influence of seasonality and anthropogenic activities on the sediment quality. Two principal component analysis (PCA) factors were obtained identifying the sampling sites affected by anthropogenic activities; Ni-Cr and Zn-Cu-V clusters were also obtained associated with stainless steel and petrochemical industrial activities. ANOVA showed the outstanding sites because of total metal concentration and significant differences among sampling sites by the acid extractable and reducible fractions for all metals except for Ba and V.     

Evaluation of electrokinetic removal of heavy metals from sewage sludge

The presence of heavy metals is one of the main obstacles for agricultural use of million tonnes of dewatered sewage sludge produced in wastewater treatment plants. Electrokinetic (EK) treatment can be applied to remove heavy metals from sludge. The aim of this study was to increase the efficiency of electrokinetic removal of heavy metals from dewatered sewage sludge. EK experiments were carried out with and without pH adjustment in cathode chamber of acidified sewage sludge. The selective sequential extraction (SSE) was used to determine the fractionation of heavy metals in sewage sludge. The mobility of heavy metals in sludge significantly increased after its acidification at pH 2.7 and followed the order: Ni, Zn, Cu, As, Cr, Pb. Removal efficiencies of heavy metals in the experiment with acidified sewage sludge and pH adjustment at cathode chamber at 2.0 were: 95% for Zn, 96% for Cu, 90% for Ni, 68% for Cr, 31% for As and 19% for Pb. The concentrations of Zn, Cu, Ni, Cr and Pb after EK treatment were below the United States Environmental Protection Agency limits for biosolids applied to agricultural land, forest, public contact sites or reclamation sites.     

Geochemical speciation and risk assessment of heavy metals in the river estuarine sediments--a case study: Mahanadi basin, India

Sequential extraction technique was used to study the mobility and dynamics of operationally determined chemical forms of heavy metals in the sediments and their ecological risk on the biotic species. The results reveal that high environmental risk of Cd, Ni, Co and Pb, are due to their higher availability in the exchangeable fraction. Substantial amount of Cd, Co, Mn, Cu, Zn, Ni and Pb, is observed as carbonate bound, which may result due to their special affinity towards carbonate and their co-precipitation with its minerals. Colloids of Fe-Mn oxides act as efficient scavengers for the heavy metals like Zn, Pb, Cu, Cr, Co, and Ni. Toxic metals like Ni, Pb and Cd are of concern, which occasionally may be associated with adverse biological effects based on the comparison with sediment quality guidelines (SQGs). The risk assessment code (RAC) suggests that the highest mobility of Cd poses a higher environmental risk and also threat to the aquatic biota. Factor analysis reveals that the enrichment of heavy metals in bioavailable fraction is mostly contributed from anthropogenic sources. These contributing sources are highlighted by cluster analysis.     

Assessment of heavy metal contamination and its mobilization from municipal solid waste open dumping site

Influence of heavy metals was investigated by conducting various tests on the samples collected from Nonthaburi dumpsite in Thailand. The heavy metal concentration in the solid waste and its mobility potential based on its binding forms was studied. The sequential extraction method was used to determine the binding forms of metals. From the analysis, Zn was found to be highest concentrated heavy metal compared to Mn, Cu, Cr, Cd, Pb, Ni and Hg in the solid waste. From the sequential extraction, Mn, Zn and Cd mostly found in reducible form, showed its susceptibility to be leached easily. Cu and Cr were found predominantly in oxidizable form and stable under anaerobic condition. Pb and Ni were present in residual form, which is inert. The estimated individual contamination factor (C(f)(i)), showed Zn with highest affinity to leach. The concentration level of all the heavy metals in the leachate except for Cr was noticed to be below the National effluent standards. Though, indicated to be safe for disposal, its effect in any concentration proved toxic to the plant life from the seed germination toxicity test using synthetic chelate ethylene diamine tetraacetic acid (EDTA).     

Extractability and phytotoxicity of heavy metals present in petrochemical industry sludge

Bioavailability of heavy metals present in industrial sludges and their subsequent phytotoxicity are crucial parameters to assess the associated health hazards and suitability for land application. The present study is an effort to determine the extractability of heavy metals present in different phases of the sludges, coming out of two different operations involved in petrochemical industry viz. spent caustic treatment (SCT) and waste water treatment (WWT) following the BCR sequential extraction procedure. The maximum amount of Cd and Cu was found associated with oxidizable phase, whereas Cr and Ni were best recovered in residual fractions of both the sludges. Maximum Pb was recovered in oxidizable and residual phase in the WWT and SCT sludges, respectively. The stabilization treatment undergone by sludges strongly influenced the heavy metal distribution and the phases to which they were associated. The total metal concentration in both the sludges did not exceed the limit set out by the European Legislation and was found as Cd = 0.449, Pb = 3.340, Ni = 6.530, Cr = 21.087, & Cu = 27.129 μg g^?1 and Cd = 0.549, Pb = 5.664, Ni = 7.161, Cr = 27.096, & Cu = 35.479 μg g^?1 in the SCT and WWT sludges, respectively. Phytotoxicity of the sludges was assessed against the germination index and the relative root and shoot growth. Sludge leachates did not adversely affect the seed germination and the early seedling growth of Mung (Phaseolus mungo) and Gram (Cicer arietinum), indicating that these metals were concentrated in the non-bioavailable fractions of sludges.     

Application of EDTA decontamination on soils affected by mining activities and impact of treatment on the geochemical partition of metal contaminants

Two soil samples were collected at mining areas located in southern Hunan Province, China. EDTA extraction of Pb, Zn, Cu and Cd from these two tailing soils was studied using column leaching experiments. The redistributions of heavy metals (HMs) were determined using the modified BCR (Community Bureau of Reference) sequential extraction procedure, before and after EDTA extraction. The results indicated that EDTA was an effective extractant because of its strong chelating ability for various HMs. The proportions of Pb, Zn, Cu and Cd in the four fractions varied largely after EDTA extraction. The extraction efficiency of EDTA of the acid-extractable fraction (AEX) was significant in shallow soil column, while in deeper soil column, decrease of the extraction efficiency of reduced (RED), oxidizable (OX) and residual fractions (RES) was obtained, which was mainly due to the decrease of EDTA concentration.     

Assessment of metals speciation in sewage sludge and stabilized sludge from different Wastewater Treatment Plants, Greater Cairo, Egypt

The metals speciation in all sludge samples from the different Wastewater Treatment Plants (WWTPs) indicated that, Mn, Ni and Zn were most abundant in the exchangeable, carbonate and Fe/Mn-oxide forms which are the easily assimilable fractions and showed the greatest degree of their mobility, while Cd, Cu, Cr and Fe were major in the organic and sulfide (exhibit some degree of mobility), and the residual form (inert phase) which, corresponds to the part of the metals which cannot be mobilized. Cement kiln dust significantly reduced the availability of metals by chemical modification of their chemical speciation into less available forms.     

Fractionation of metals in street sediment samples by using the BCR sequential extraction procedure and multivariate statistical elucidation of the data

The concentrations of metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in street sediment samples were determined by flame atomic absorption spectrometry (FAAS) using the modified BCR (the European Community Bureau of Reference) sequential extraction procedure. According to the BCR protocol for extracting the metals from the relevant target phases, 1.0 g of specimen of the sample was treated with 0.11 M acetic acid (exchangeable and bound to carbonates), 0.5M hydroxylamine hydrochloride (bound to iron- and manganese-oxides), and 8.8M hydrogen peroxide plus 1M ammonium acetate (bound to sulphides and organics), sequentially. The residue was treated with aqua regia solution for recovery studies, although this step is not part of the BCR procedure. The mobility sequence based on the sum of the BCR sequential extraction stages was: Cd approximately Zn ( approximately 90%)>Pb ( approximately 84%)>Cu ( approximately 75%)>Mn ( approximately 70%)>Co ( approximately 57%)>Ni ( approximately 43%)>Cr ( approximately 40%)>Fe ( approximately 17%). Enrichment factors as the criteria for examining the impact of the anthropogenic emission sources of heavy metals were calculated, and it was observed that the highest enriched elements were Cd, Pb, and Zn in the dust samples, average 190, 111, and 20, respectively. Correlation analysis (CA) and principal component analysis (PCA) were applied to the data matrix to evaluate the analytical results and to identify the possible pollution sources of metals. PCA revealed that the sampling area was mainly influenced from three pollution sources, namely; traffic, industrial, and natural sources. The results show that chemical sequential extraction is a precious operational tool. Validation of the analytical results was checked by both recovery studies and analysis of the standard reference material (NIST SRM 2711 Montana Soil).     

Chemical fractionation and translocation of heavy metals in Canna indica L. grown on industrial waste amended soil

A pot experiment was carried out to assess the effect of different amendments of industrial sludge on the growth of Canna indica L. as well as the translocation potential of heavy metals of this plant. The accumulation of metals (Cr, Fe, Cd, Cu, Ni, Zn, Mn and Pb) in different parts of C. indica L. grown on industrial sludge-amended soil increased with time and increasing doses of sludge amendments. Sequential extraction method was followed to estimate the different fractions of heavy metals in sludge-amended soils collected from different periods of this study. The results showed that Mn, Zn, Cd, Cr and Pb were mostly associated with Fe–Mn oxide fraction in all amendments, whereas, Ni was mostly found in residual (RES) fraction. Cu and Fe were found to be higher in organically bounded form (OM) and RES fraction. The metal concentration in C. indica L. after 90 days of experiment started, was in the order of Fe > Cr > Mn > Zn > Ni > Cu > Cd > Pb and the metal translocation was found lesser in shoot. With the increasing percentage of sludge amendments in soil the metal concentrations increased in different parts of plants. Overall, the plant C. indica L. was found to be well adapted in industrial sludge amendments and it may be recommended that this plant was found suitable for phytoremediation of most of the studied metals.