PAH removal from spiked municipal wastewater sewage sludge using biological, chemical and electrochemical treatments

Polycyclic aromatic hydrocarbons (PAHs) have been widely studied due to their presence in all the environmental media and toxicity to life. These molecules are strongly adsorbed on the particulate matters of soils, sludges or sediments because of their strong hydrophobicity which makes them less bioavailability, thus limiting their bioremediation. Different sludge treatment processes were tested to evaluate their performances for PAH removal from sludge prealably doped with 11 PAHs (5.5mg each PAH kg(-1) of dry matter (DM)): two biological processes (mesophilic aerobic digestion (MAD) and simultaneous sewage sludge digestion and metal leaching (METIX-BS)) were tested to evaluate PAH biodegradation in sewage sludge. In parallel, two chemical processes (quite similar Fenton processes: chemical metal leaching (METIX-AC) and chemical stabilization (STABIOX)) and one electrochemical process (electrochemical stabilization (ELECSTAB)) were tested to measure PAH removal by these oxidative processes. Moreover, PAH solubilisation from sludge by addition of a nonionic surfactant Tween 80 (Tw80) was also tested. The best yields of PAH removal were obtained by MAD and METIX-BS with more than 95% 3-ring PAH removal after a 21-day treatment period. Tw80 addition during MAD treatment increased 4-ring PAHs removal rate. In addition, more than 45% of 3-ring PAHs were removed from sludge by METIX-AC and during ELECSTAB process were quiet good with approximately 62% of 3-ring PAHs removal. However, little weaker removal of 3-ring PAHs (<35%) by STABIOX. None of the tested processes were efficient for the elimination of high molecular weight (> or = 5-ring) PAHs from sludge.     

Zinc-copper interaction affecting plant growth on a metal-contaminated soil

In order to assess the effects of metal interactions on plant growth, a greenhouse experiment was conducted, in which spring barley was grown for 48 days in a soil to which cadmium, copper, lead and zinc were added singly and in combination. Plant growth was measured as shoot and root dry matter production. At the end of the experiment the plant material was analysed for metal uptake and the soil was extracted with CaCl(2) solution, to measure the plant-available metal content. The most consistent effect on plant growth was an interaction between copper and zinc, which was also important in determining uptake of these metals and the amounts extractable with CaCl(2) solution. An analysis of the underlying mechanism led to the conclusion that the growth of barley was controlled principally by the amount of plant-available zinc, which depended on the amounts of both added zinc and added copper. The effect of the added copper was to increase the toxicity of the added zinc.     

Heavy metal speciation and mobility assessment of arid soils in the vicinity of Al Ain landfill, United Arab Emirates

Sixty-four surface soil samples taken in the vicinity of Al Ain landfill were analysed for cadmium, chromium, copper, nickel, lead and zinc by inductively coupled plasma spectroscopy. Extraction techniques were used to establish the association of the total concentrations of the six metals in the soil samples with their contents in the exchangeable, carbonate, iron/manganese oxides, and residual fractions. In the investigated soils, the recorded concentrations were as follows: 0.043 mg kg^-1 for cadmium, 19.1 mg kg^-1 for chromium, 53.3 mg kg^-1 for copper, 60 mg kg^-1 for nickel, 13.7 mg kg^-1 for lead, and 117 mg kg^-1 for zinc. Cadmium, chromium, nickel, lead and zinc concentrations in the investigated soil samples reflect the natural background values in shale, whereas copper is slightly enriched. I-geo (geoaccumulation index) values of the metals in the soils under study indicate that they are uncontaminated with cadmium, chromium, nickel, lead and zinc, but contaminated to moderately contaminated with copper. Heavy metal contents in the sediments were found to be significantly influenced by different physico-chemical parameters. The effect of these parameters can be arranged in the following order: clay fraction > carbonate fraction > silt fraction > organic matter fractions. A sequential extraction procedure showed that the total concentrations of the heavy metals are largely bound to the residual phase (retained 71.4% of cadmium, 77.8% of chromium, 75% of copper, 47% of nickel, 62.8% of lead, and 75.8% of zinc). A likely sequence of mobility in the investigated soils is as follows: chromium > lead > nickel > cadmium > zinc > copper.     

污泥果肥利用中重金属迁移特征研究

为了厦门城市污泥的安全利用，将石渭头污水处理厂污泥经过好氧堆肥后施用于柚子树，对重金属元素在土壤、树叶及果肉中的迁移特征进行了研究。结果表明：Cd在土壤中的富集能力强；重金属元素从土壤向树叶迁移累积能力比向果肉的大得多，污泥肥料不能用于叶类食用植物的施用；Cr向树叶、Ni向果肉的迁移累积能力强；泥肥的施用加重了土壤中Cd的污染，提高了Cr向树叶、Ni向果肉的迁移能力；污泥果肥利用需降低Ni的浓度，对污泥中含量较高的Cu、Zn、Ni、Cr和Cd需进行跟踪检测。     

The influence of salinity on metal uptake and effects in the midge Chironomus maddeni

The influence of different porewater salinities (up to 12 g/L) on the toxicity and bioaccumulation of copper, zinc and lead from metal-spiked sediments was assessed using the midge, Chironomus maddeni. Survival of the larvae was significantly reduced at a porewater salinity of 12 g/L, but no effects were observed at 4 or 8 g/L. Both growth and survival of C. maddeni were reduced after exposure to salt/metal spiked sediments as compared to those exposed to sediments spiked with metals or salt alone. Increased salinity resulted in increased bioaccumulation of copper and zinc, but decreased bioaccumulation of lead. The observed patterns of bioaccumulation were not entirely explained by the modelled free ion activities of the metals, indicating that factors such as osmotic stress, consumption of metal-contaminated sediments or metal interactions may have been important as well. These results highlight the need to consider the influence of existing or potential salinization when undertaking hazard assessments of freshwater systems impacted by contaminants such as trace metals.     

Risk assessment of linear alkylbenzene sulphonates, LAS, in agricultural soil revisited: robust chronic toxicity tests for Folsomia candida (Collembola), Aporrectodea caliginosa (Oligochaeta) and Enchytraeus crypticus (Enchytraeidae)

To obtain robust data on the toxicity of LAS, tests with the collembolan Folsomia candida L., the oligochaetes Aporrectodea caliginosa Savigny (earthworm) and Enchytraeus crypticus Westheide and Graefe (enchytraeid) were performed in a sandy loam soil. Additionally limited tests with LAS spiked to sewage sludge, and subsequently mixed into soil, were performed. For the endpoint of interest, reproduction in soil, we found an EC10 of 205 mg LAS kg(-1) soil [8.6-401] [95% confidence limits] for F. candida and an EC10 of 46 mg LAS kg(-1) soil [13-80] for A. caliginosa after 28 days. E. crypticus was not affected by concentrations up to 120 mg LAS kg(-1) soil. When adding (low contaminated) non-spiked sludge to soil, high stimulation of reproduction was observed for E. crypticus and A. caliginosa but not for F. candida. We argue that this difference in stimulative response between the tested species is related to the difference in feeding behaviour. Sludge spiked with LAS did not significantly affect the reproduction of F. candida (fertility: number of juvenile offspring) and A. caliginosa (fecundity: number of cocoons) (dose equivalent to 181 g and 91 g LAS kg(-1) sludge, respectively). Significantly reduced reproduction was observed for E. crypticus (at 120 mg LAS kg(-1) soil+sludge corresponding to 72 g LAS kg(-1) sludge) compared to non-spiked sludge. The reproduction by E. crypticus was, however, comparable to the reproduction observed in the control soil without sludge. Compared to LAS directly spiked to soil, the reproductive output of organisms exposed to spiked sludge was either not significantly different (F. candida, E. crypticus) or significantly improved (A. caliginosa). More studies are needed in order to make firm conclusions on the potential effect of artificially contaminated sludge in soil systems.     

Use of oxygen consumption and ammonium excretion to evaluate the sublethal toxicity of cadmium and zinc on Litopenaeus schmitti (Burkenroad, 1936, Crustacea).

Penaeid shrimps are important resources for worldwide fisheries and aquaculture. In Brazil, Litopenaeus schmitti (L. schmitti) is a important commercially exploited species and is an ideal animal for studying the impairment caused by the effects of heavy metals that are often detected in coastal areas. The main purpose of the present study was to detect the acute toxicity of cadmium and zinc to L. schmitti and investigate their effects on oxygen consumption and ammonium excretion, investigations that have not been carried out in this species before. First, the acute toxicity of cadmium and zinc to L. schmitti 24, 48, 72, and 96-hour medium lethal concentration was examined, which resulted in the following values: 0.98, 0.54, 0.32, and 0.18 mg/L for cadmium and 1.64, 1.22, 0.86, and 0.31 mg/L for zinc. Furthermore, we also found that exposure of shrimp to cadmium and zinc caused an inhibition in oxygen consumption of 55.92 and 44.09%, respectively, relative to the control. However, after separate exposure to cadmium and zinc, elevations in ammonium excretion were obtained, which were 174.28 and 162.5% higher than the control, respectively.     

The induction of metallothionein in tissues of the Norway lobster Nephrops norvegicus following exposure to cadmium, copper and zinc: the relationships between metallothionein and the metals

Nephrops norvegicus were exposed simultaneously to cadmium, copper and zinc over an 18-day period. Exposure concentrations were control, 1, 5 and 25 microg litre(-1) for cadmium and copper and 8, 40 and 200 microg litre(-1) for zinc. Concentrations of cadmium, copper, zinc and metallothionein were measured in homogenates of both the gill and the hepatopancreas. Quantification of metallothionein was carried out by differential pulse polarography. Cadmium concentrations increased significantly in the gill and hepatopancreas of both male and female animals in response to increases in exposure concentration. In contrast, the concentration of copper and zinc increased significantly in the gills of males, but not in females. In the hepatopancreas, neither copper nor zinc resulted in significant changes in concentrations of these metals. Metallothionein concentrations in the gill and hepatopancreas were increased significantly in relation to metal exposure in both males and females. Concentrations of cadmium and metallothionein in both the gill and hepatopancreas of males and females were positively correlated. Copper in the hepatopancreas also showed positive relationships with MT concentrations in males, but not in females. This study suggested that cadmium MTs in the gill and hepatopancreas of Nephrops norvegicus could be used as a sensitive tool to detect cadmium contamination in the lobsters, although this was not true for copper and zinc.     

Effect of heavy metals on earthworm activities during vermicomposting of municipal solid waste.

The effect of heavy metals on the activities of earthworm species Eudrillus eugineae was studied during vermicomposting of municipal solid waste (MSW) spiked with heavy metals. The activities of earthworms, in terms of growth and biomass production and number of cocoons produced, were monitored periodically, and the concentration of heavy metals in earthworms and substrates was determined at definite intervals. Laboratory-scale experiments were performed by mixing individual heavy metals in MSW. Copper, cadmium, chromium, lead, and zinc were selected for the study. The study concludes that heavy metals tend to accumulate in the body of earthworms; hence, the inherent concentration of heavy metals in the substrate before vermicomposting must be considered in view of composting of MSW and its application to soil. It was observed that copper and cadmium were toxic for the worms at 1.5 and 0.1 g/kg of the waste, respectively. The studies also suggest that earthworms are susceptible to the free form of heavy metals. Cadmium is the most toxic metal, followed by copper. Based on the investigation and observation, it was also found that earthworms should be separated from castings before the use of castings in soil amendments.     

Distribution of copper, lead, cadmium and zinc concentrations in soils around Kabwe town in Zambia

The extent of pollution of the environment as a result of mining activities in Kabwe, the provincial capital of Central province in Zambia has not yet been evaluated. Mining of lead and zinc were the core activities of Kabwe mine while cadmium and silver were produced as by-products. The smelting processes produced a significant amount of copper. The spatial distribution of four heavy metals in soils in the northern, eastern, southern and western directions of the mine was analyzed using atomic absorption spectrometry (AAS). Samples were collected up to 20 km in each direction from the mine. Results were consistent with the wind flow patterns in the town. Results ranged between 0.08 and 28 mg kg(-1) (Cd); 0.20 and 0.61 mg kg(-1) (Cu); 0.10 and 758 mg kg(-1) (Pb) and 0.40 and 234 mg kg(-1) (Zn) suggesting high precipitation of metals from the core mining activities. These concentrations were for only the fractions of metals extractable by 0.5M nitric acid and that could be available for plant uptake in the environment. The distribution of metals indicated a decrease of metal concentrations with distance from the mine, which confirmed that precipitation due to mining activities was the main cause of soil contamination.     

Multi-generation toxicity of zinc, cadmium, copper and lead to the potworm Enchytraeus albidus

In standard chronic terrestrial toxicity tests with invertebrates, adult organisms are exposed to the contaminants and the number of offspring is quantified. These procedures do not allow the assessment of possible effects on all life stages of the organism, which may lead to an underestimation of the toxicity of the test substance. To evaluate the importance of this issue, the potworm Enchytraeus albidus was exposed to zinc, cadmium, copper and lead for two subsequent generations. Juvenile production was assessed for both generations. Considering the variability of metal toxicity data reported in the literature, it is concluded that the two generation assay did not markedly increase the sensitivity of the standard E. albidus test for the tested metals. Therefore, toxicity data obtained with the proposed test guideline with E. albidus are protective for all life stages.     

Hybrid process for heavy metal removal from wastewater sludge.

Bioleaching processes have been demonstrated to be effective technologies in removing heavy metals from wastewater sludge, but long hydraulic retention times are typically required to operate these bioprocesses. A hybrid process (coupling biological and chemical processes) has been explored in laboratory pilot-scale experiments for heavy metals (cadmium [Cd], copper [Cu], chromium [Cr], and zinc [Zn]) removal from three types of sludge (primary sludge, secondary activated sludge, and a mixture of primary and secondary sludge). The hybrid process consisted of producing a concentrate ferric ion solution followed by chemical treatment of sludges. Ferric iron solution was produced biologically via oxidation of ferrous iron by A. ferrooxidans in a continuous-flow stirred tank (5.2 L) reactor (CSTR). Wastewater sludge filtrate (WSF) containing nutrients (phosphorus and nitrogen) has been used as culture media to support the growth and activity of indigenous iron-oxidizing bacteria. Results showed that total organic carbon (TOC) concentrations of the culture media in excess of 235 mg/L were found to be inhibitory to bacterial growth. The oxidation rate increased as ferrous iron concentrations ranged from 10 to 40 g Fe2+/L. The percentage of ferrous iron (Fe2+) oxidized to ferric iron (Fe3+) increased as the hydraulic retention time (HRT) increased from 12 to 48 h. Successful and complete Fe2+ oxidation was recorded at a HRT of 48 h using 10 g Fe2+/L. Subsequently, ferric ion solution produced by A. ferrooxidans in sludge filtrate was used to solubilize heavy metals contained in wastewater sludge. The best solubilization was obtained with a mixture of primary and secondary sludge, demonstrating a removal efficiency of 63, 71, 49, and 80% for Cd, Cu, Cr, and Zn, respectively.     

Effects of pH on the toxicity of cadmium, copper, lead and zinc to Folsomia candida Willem, 1902 (Collembola) in a standard laboratory test system

EC₅₀s for cadmium, copper, lead and zinc were determined for juvenile production of Folsomia candida at pH6.0, 5.0 and 4.5 in a standard laboratory test system. In contrast to most previous studies where metal toxicity was increased at low pHs, in our experiments there was no clear relationship between soil acidity and EC_{50-reproduction} in this species. The EC_{50-reproduction} values (μg g⁻¹) for cadmium and zinc were similar at all three pHs (pH6.0: Cd 590, Zn 900; pH5.0: Cd 780, Zn 600; pH4.5: Cd 480, Zn 590). In contaminated field sites adjacent to primary zinc smelters, zinc is invariably present in soils at concentrations of at least 50 times that of cadmium Thus deleterious effects of mixtures of these metals on populations of Collembola in such sites can be attributed to zinc rather than cadmium.     

Effect of mixed cadmium,copper, nickel and zinc at different pHs upon alfalfa growth and heavy metal uptake

Alfalfa plants were grown in soil-pots contaminated with a mixture of Cd(II), Cu(II), Ni(II), and Zn(II), (at 50 mg/kg each) at pHs of 4.5, 5.8, and 7.1. The plants were fertilized using a nutrient solution, which was adjusted appropriately to the same pH. Plants in the control treatment were grown in the absence of the heavy metals mixture. The growth of the control plants was the same at the three pHs studied and the heavy metal stressed plants also showed similar behavior at each pHs. There were statistically significant differences (P<0.05) between the shoot length of the control treatment plants and the length of plants grown in the presence of the heavy metal mixture. Under the effects of the heavy metal mixture, nickel was the most accumulated element in the shoot tissue, with 437, 333, and 308 ppm at pH 7.1, 5.8, and 4.5, respectively. Cadmium was found to be second in accumulated concentrations with 202 ppm, 124 ppm, and 132 ppm at pH 7.1, 5.8, and 4.5, respectively, while zinc was third, followed by copper. The maximum relative uptakes (element in plant/element in soil-water-solution) were found to be 26 times for nickel, 23 times for cadmium, 12 times for zinc. and 6 times for copper. We considered these relations as indicative of the ability of alfalfa plants to take up elements from a soil matrix contaminated with a mixture of cadmium, copper, nickel, and zinc.     

Palygorskite as a feasible amendment to stabilize heavy metal polluted soils

The sorption behaviour of palygorskite has been studied with respect to lead, copper, zinc and cadmium in order to consider its application to remediate soils polluted with these metals. The Langmuir model was found to describe well the sorption processes offering maximum sorption values of 37.2 mg/g for lead, 17.4 mg/g for copper, 7.11 mg/g for zinc and 5.83 mg/g for cadmium at pH 5-6. In addition the effect of palygorskite amendment in a highly polluted mining soil has been studied by means batch extractions and leaching column studies. The soluble metal concentrations as well as the readily-extractable metal concentrations were substantially decreased at any concentration of palygorskite applied to soil (1, 2, 4%), although the highest decrease is obtained at the 4% dose. The column studies also showed a high reduction in the metal leaching (50% for lead, 59% for copper, 52% for zinc and 66% for cadmium) when a palygorskite dose of 4% was applied.     

Change of PCBs and forms of heavy metals in sewage sludge during thermophilic anaerobic digestion

Determination of seven congeners of PCBs was carried out for sewage sludge before, during and after thermophilic digestion. The overall content of heavy metals (Zn, Cu, Ni, Cd, Pb, Cr) in sludge before and after digestion was determined. Moreover the concentration of heavy metals in particular chemical fractions of the sludge was analyzed. After the thermophilic digestion total concentration of seven PCBs was reduced by 47%, which suggests that thermophilic digestion affects PCB reduction positively. On the 10th d of the process, concentration of lower chlorinated PCBs increased, whereas those of higher chlorinated PCBs decreased. The thermophilic digestion process showed no accumulation of the studied heavy metals in the mobile fractions (exchangeable and carbonate) of the stabilized sewage sludge, except for nickel. The highest increase in zinc, copper, cadmium, and chromium concentration was observed in the organic-sulfide fraction, whereas the highest increase in lead was found in the residual fraction of the sludge. In case of nickel both fractions of organic-sulfide and exchangeable-carbonate fractions were enriched.     

Models for the field-based toxicity of copper and zinc salts to wheat in 11 Australian soils and comparison to laboratory-based models

Laboratory-based relationships that model the phytotoxicity of metals using soil properties have been developed. This paper presents the first field-based phytotoxicity relationships. Wheat (Triticum aestivum L.) was grown at 11 Australian field sites at which soil was spiked with copper (Cu) and zinc (Zn) salts. Toxicity was measured as inhibition of plant growth at 8 weeks and grain yield at harvest. The added Cu and Zn EC10 values for both endpoints ranged from approximately 3 to 4760 mg/kg. There were no relationships between field-based 8-week biomass and grain yield toxicity values for either metal. Cu toxicity was best modelled using pH and organic carbon content while Zn toxicity was best modelled using pH and the cation exchange capacity. The best relationships estimated toxicity within a factor of two of measured values. Laboratory-based phytotoxicity relationships could not accurately predict field-based phytotoxicity responses.     

The fate of trace metals during the metamorphosis of chironomids (diptera, chironomidae)

The fate of the trace metals zinc, cadmium and copper during the metamorphosis of chironomids was studied under field and experimental conditions. Field observations demonstrated a significant decrease in the trace metal body burden of larvae and imagines of Stictochironomus histrio Fabricius. No such difference were noted between successive developmental stages of Chironomus anthracinus Zett. The exuviae of both species contained small amounts of trace metals. Experiments, in which larvae of S. histrio and C. riparius Meigen were individually exposed, showed that larvae of both species accumulated substantial amounts of zinc and cadmium. For these metals, a transfer to pupae and imagines occurred. However, pupae had a lower body burden than larvae, and imagines a lower body burden than the pupae. Copper was also accumulated in the larvae, but it was excreted almost completely before the pupal stage. Elimination pathways of the trace metals during metamorphosis and the ecotoxicological consequences of trace metal transfer are discussed.     

The toxicity of copper,cadmium and zinc to four different Hydra (Cnidaria: Hydrozoa)

An acute toxicity study of three metals to Hydra species carried out using two different assessment methods, (i) determination of the LC50 and (ii) measurement of progressive morphological changes, demonstrated that relative toxicity decreased from copper to cadmium with zinc the least toxic for all species. The latter method revealed more details of the effect on Hydra in terms of physical damage to the polyp but both methods indicated that H. viridissima was more sensitive to copper and cadmium than H. vulgaris¹ (Zurich strain, male clone), H. vulgaris² (a dioecious strain reproducing sexually and asexually) and H. oligactis (dioecious, reproducing sexually and asexually). The responses to zinc were similar for all Hydra. The possible role of metabolic interactions between H. viridissima and its symbiotic green algae in contributing to the greater sensitivity of this polyp is discussed.     

Heavy metal binding by the polymeric organic fractions of sewage sludges

Organic complexes in sewage sludge play an important role in the speciation and transformation of metals into potentially more toxic and bioavailable forms. Two organic fractions, bacterial extracellular polymer and fulvic acid, were extracted from mixed liquor and digested sewage sludge by methods established as the most appropriate. The homogeneity of the extracts was verified using gel permeation chromatography. Conditional stability constants and complexation capacities of the organic fractions from the sludges with copper, cadmium, nickel and zinc have been determined using equilibrium dialysis titration. Organic fractions extracted from digested sludge demonstrated a greater capacity to complex metals over mixed liquor extracts. Copper formed stronger complexes than nickel with the mixed liquor biomass and cadmium exhibited the greatest affinity for digested sludge organic matter.