Influence of soil properties on heavy metal sequestration by biochar amendment: 1. Copper sorption isotherms and the release of cations

The amendment of carbonaceous materials such as biochars and activated carbons is a promising in situ remediation strategy for both organic and inorganic contaminants in soils and sediments. Mechanistic understandings in sorption of heavy metals on amended soil are necessary for appropriate selection and application of carbonaceous materials for heavy metal sequestration in specific soil types. In this study, copper sorption isotherms were obtained for soils having distinct characteristics: clay-rich, alkaline San Joaquin soil with significant heavy metal sorption capacity, and eroded, acidic Norfolk sandy loam soil having low capacity to retain copper. The amendment of acidic pecan shell-derived activated carbon and basic broiler litter biochar lead to a greater enhancement of copper sorption in Norfolk soil than in San Joaquin soil. In Norfolk soil, the amendment of acidic activated carbon enhanced copper sorption primarily via cation exchange mechanism, i.e., release of proton, calcium, and aluminum, while acid dissolution of aluminum cannot be ruled out. For San Joaquin soil, enhanced copper retention by biochar amendment likely resulted from the following additional mechanisms: electrostatic interactions between copper and negatively charged soil and biochar surfaces, sorption on mineral (ash) components, complexation of copper by surface functional groups and delocalized π electrons of carbonaceous materials, and precipitation. Influence of biochar on the release of additional elements (e.g., Al, Ca) must be carefully considered when used as a soil amendment to sequester heavy metals.     

Acute effects of Fe₂O₃, TiO₂, ZnO and CuO nanomaterials on Xenopus laevis

Metal oxide nanomaterials have exhibited toxicity to a variety of aquatic organisms, especially microbes and invertebrates. To date, few studies have evaluated the toxicity of metal oxide nanomaterials on aquatic vertebrates. Therefore, this study examined effects of ZnO, TiO₂, Fe₂O₃, and CuO nanomaterials (20-100 nm) on amphibians utilizing the Frog Embryo Teratogenesis Assay Xenopus (FETAX) protocol, a 96 h exposure with daily solution exchanges. Nanomaterials were dispersed in reconstituted moderately hard test medium. These exposures did not increase mortality in static renewal exposures containing up to 1000 mg L⁻¹ for TiO₂, Fe₂O₃, CuO, and ZnO, but did induce developmental abnormalities. Gastrointestinal, spinal, and other abnormalities were observed in CuO and ZnO nanomaterial exposures at concentrations as low as 3.16 mg L⁻¹ (ZnO). An EC₅₀ of 10.3 mg L⁻¹ ZnO was observed for total malformations. The minimum concentration to inhibit growth of tadpoles exposed to CuO or ZnO nanomaterials was 10 mg L⁻¹. The results indicate that select nanomaterials can negatively affect amphibians during development. Evaluation of nanomaterial exposure on vertebrate organisms are imperative to responsible production and introduction of nanomaterials in everyday products to ensure human and environmental safety.     

Structure-activity relationships of larvicidal monoterpenes and derivatives against Aedes aegypti Linn

In the search for larvicidal compounds against Aedes aegypti L. (Diptera: Culicidae), a collection of monoterpenes were selected and evaluated. R- and S-limonene exhibited the highest larvicidal potency (LC₅₀ = 27 and 30 ppm, respectively), followed by γ-terpinene (LC₅₀ = 56 ppm) and RS-carvone (LC₅₀ = 118 ppm). Structural characteristics which may contribute to the understanding of the larvicidal activity of monoterpenes were empirically identified. The presence of heteroatoms in the basic hydrocarbon structure decreases larvicidal potency. Conjugated and exo double bonds appear to increase larvicidal potency. Replacement of double bonds by more reactive epoxides decreases the larvicidal potency. The presence of hydroxyls in the cyclic structure resulted in decreased potency, probably due to increased polarity indicanting that lipophilicity seems to play an important role in increasing the larvicidal potency in this set of compounds.     

Long-term records of cadmium and silver contamination in sediments and oysters from the Gironde fluvial-estuarine continuum - evidence of changing silver sources

The Gironde fluvial estuarine system is impacted by historic metal pollution (e.g. Cd, Zn, Hg) and oysters (Crassostrea gigas) from the estuary mouth have shown extremely high Cd concentrations for decades. Based on recent work (Chiffoleau et al., 2005) revealing anomalously high Ag concentrations (up to 65 mg kg⁻¹; dry weight) in Gironde oysters, we compared long-term (∼1955-2001) records of Ag and Cd concentrations in reservoir sediment with the respective concentrations in oysters collected between 1979 and 2010 to identify the origin and historical trend of the recently discovered Ag anomaly. Sediment cores from two reservoirs upstream and downstream from the main metal pollution source provided information on (i) geochemical background (upstream; Ag: ∼0.3 mg kg⁻¹; Cd: ∼0.8 mg kg⁻¹) and (ii) historical trends in Ag and Cd pollution. The results showed parallel concentration-depth profiles of Ag and Cd supporting a common source and transport. Decreasing concentrations since 1986 (Cd: from 300 to 11 mg kg⁻¹; Ag: from 6.7 to 0.43 mg kg⁻¹) reflected the termination of Zn ore treatment in the Decazeville basin followed by remediation actions. Accordingly, Cd concentrations in oysters decreased after 1988 (from 109 to 26 mg kg⁻¹, dry weight (dw)), while Ag bioaccumulation increased from 38 up to 116 mg kg⁻¹, dw after 1993. Based on the Cd/Ag ratio (Cd/Ag ∼ 2) in oysters sampled before the termination of zinc ore treatment (1981-1985) and assuming that nearly all Cd in oysters originated from the metal point source, we estimated the respective contribution of Ag from this source to Ag concentrations in oysters. The evolution over the past 30 years clearly suggested that the recent, unexplained Ag concentrations in oysters are due to increasing contributions (>70% after 1999) by other sources, such as photography, electronics and emerging Ag applications/materials.     

Improvement of Vicia-micronucleus test for assessment of soil quality: a proposal for international standardization

The Viciafaba root tip micronucleus test is one of the most employed plant genotoxicity assays, and has been used on various types of contaminated materials. This test has been standardized by AFNOR, the French member organization of ISO. However, this test is usually performed with a water extraction step but soil genotoxicity assessment would be more relevant when performed directly in the soil itself. In order to harmonize these protocols, an ISO standard for the V.faba micronucleus test in both liquid phase (exposure of plants to different liquid matrix, including soil water extracts) and solid phase (direct exposure of plants to the soil) would be very useful. In this context, we compared two exposure durations in the solid phase (48 h and 5 d) for the V.faba micronucleus test with two different well-known genotoxicants, maleic hydrazide and copper sulfate. We concluded that these two durations induced equivalent sensitivity: the micronucleus frequency was significantly increased with 5 μmol maleic hydrazide per kg dry soil and with 2 mmol copper sulfate per kg dry soil with both exposure durations. However, exposing roots to soil during 48 h is more practical. Moreover, organically and conventionally cultured seeds were employed to determine whether the seed provenance influenced the test sensitivity. Organic seeds were less sensitive to copper, possibly because copper-based treatments are permitted, and often applied, in organic farms. Therefore, in the absence of completely non-treated seeds, organically-cultured seeds did not appear to offer any advantages over conventional seeds.     

Levels and trends of PCDD/Fs and PCBs in camel milk (Camelus bactrianus and Camelus dromedarius) from Kazakhstan

To date, despite the fact it represents a very important part of the national dairy production, no data are available concerning the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) in camel milk from the Republic of Kazakhstan. Selected PCDDs, PCDFs, and PCBs were measured in pools of milk from camels (n=15) located in various places of Kazakhstan (Almaty, Atyrau, Aralsk, Shymkent) and sampled at two different seasons for two different species (Camelus bactrianus and Camelus dromedarius). Non-dioxin-like (NDL-)PCB concentrations (6.3±2.7 ng g(-1) fat, median 5.1 ng g(-1) fat, range 0.6-17.4 ng g(-1) fat) were far below the maximum value of 40 ng g(-1) fat proposed by the EU. Dioxin-like (DL-)PCB concentrations (1.7±0.7 ng g(-1) fat, median 1.5 ng g(-1) fat, range 0.3-4.2 ng g(-1) fat) and the NDL-PCB to DL-PCB ratio (4.3) were similar to what is reported in EU for cow-based dairy products. PCB 52 and PCB 101 appeared to be proportionally more present in Kazakh camel milk samples (>60% of the sum of the 6 indicator NDL-PCBs) than in European cow milk samples (<10% of the sum of the 6 indicator NDL-PCBs), indicating possible differences in the route of exposure to PCBs in Kazakhstan. PCB 105 and PCB 118 appeared to be present at higher concentrations in camel milk (>80% of the sum of the 12 DL-PCBs). PCB 105, PCB 118 and PCB 156 were the major congeners for DL-PCBs, accounting for 92% of the sum of concentrations of DL-PCBs (88% for Belgian cows). In terms of TEQ, PCB 126 and PCB 118 are the major contributors and represent, respectively, 80% and 14% of the DL-PCB TEQWHO05 concentrations. No significant interracial or geographical trends were observed for NDL- and DL-PCB profiles. However, concentrations of all DL-PCBs appeared to be significantly higher for samples collected in Atyrau region. 2,3,7,8-TCDD level (mean 0.08±0.07 pg g(-1) fat, median 0.08 pg g(-1) fat, range 0.00-0.18 pg g(-1) fat, 60%>LOQs) were very low for all samples and 2,3,4,7,8-PeCDF was the major contributor (27%) to the PCDD/F TEQWHO05. Considering the total TEQWHO05 (sum of DL-PCBs and PCDD/Fs), DL-PCB and PCDD/F contributed for 73% and 27%, respectively. A decrease of only 1% of the total TEQ was observed when using the TEFWHO05 scale instead of the TEFWHO98 scale. Two samples collected in the region of Atyrau exceeded the EU maximum level value of 6.00 pg TEQWHO98 g(-1) fat (6.4 pg TEQWHO05 g(-1) fat and 6.9 pg TEQWHO05 g(-1) fat). Both samples exceeded the EU action level for the sum of DL-PCBs. Based on the fact that camel milk is used to prepare popular traditional fermented drinks like shubat, this suggests that the human exposure in the Caspian Sea region of Atyrau should be expected to be higher than in the other regions studied here.     

Heavy metal accumulation in Halimione portulacoides: intra- and extra-cellular metal binding sites

Salt marsh plants can sequestrate and inherently tolerate high metal concentrations found in salt marsh sediments. This work intended to understand the Halimione portulacoides (L.) Aellen strategies to prevent metal toxicity, by investigating the metal location in different plant organs and in the cell. A sequential extraction was performed on leaves, stems and roots of H. portulacoides in order to determine and compare the metal (Zn, Pb, Co, Cd, Ni and Cu) concentration in several fractions of the plant material (ethanolic, aqueous, proteic, pectic, polissacaridic, lenhinic and cellulosic). This study shows that all plant organs of H. portulacoides mostly retain metals in the cell wall (65% is the average for all studied metals stored in the root cell wall, 55% in the stems and 53% in the leaves), and the metal content in the intracellular compartment is much lower (21% in roots, 25% in stems and 32% in leaves). High levels of heavy metal in the sedimentary environment do not cause toxicity to H. portulacoides, because H. portulacoides immobilizes them in different cell compartments (cell wall+proteic fraction+intracellular) outside key metabolic sites.     

Effectiveness of electrocoagulation process in removing organic compounds from slaughterhouse wastewater using monopolar and bipolar electrolytic cells

Slaughterhouse wastewaters contain varied and high amounts of organic matter (e.g., proteins, blood, fat). In order to produce an effluent suitable for stream discharge, electrochemical techniques have been particularly explored at the laboratory pilot scale for organic compounds removal from poultry slaughterhouse (PS) effluent. Electrocoagulation (EC) process was tested using either mild steel or aluminium electrodes arranged in bipolar (BP) or monopolar configuration system. Results showed that the best performance was obtained using mild steel BP electrode system operated at a current intensity of 0.3A, through 60 or 90 min of treatment. Under these conditions, removals of 86+/-1% and 99+/-1% were measured for BOD and oil and grease, respectively, whereas soluble COD and total COD were removed by 50+/-4% and 82+/-2%, respectively. EC is also efficient for decolorization (red-color) and clarification of the PS effluent. Removals of 89+/-4% and 90+/-4% have been measured for total suspended solids and turbidity, respectively. Electrochemical coagulation operated under the optimal conditions involves a total cost of 0.71 USD $ per cubic meter of treated PS effluent. This cost includes energy and electrode consumptions, chemicals, and sludge disposal.     

Sublethal ammonia exposure of Nile tilapia (Oreochromis niloticus L.): effects on gill, liver and kidney histology

The effects of exposures to sublethal ammonia concentrations on Nile tilapia (Oreochromis niloticus L.) were determined with respect to histology. The experiments were conducted for six weeks and with four different ammonia concentrations (control, 1, 2, 5, 10 mg l(-1) TA-N). Fish exposed to different ammonia concentrations displayed histopathologic alterations in the gills, liver and kidney. Gill tissues displayed hyperemia, chloride cell proliferation, fusion in secondary lamella, telangiectasis. Liver tissue revealed cloudy swelling and hydropic degeneration, whereas in kidney tissues hyperemia and glomerulonephritis were observed.     

Occurrence, fate and antibiotic resistance of fluoroquinolone antibacterials in hospital wastewaters in Hanoi, Vietnam

Occurrence and behavior of fluoroquinolone antibacterial agents (FQs) were investigated in hospital wastewaters in Hanoi, Vietnam. Hospital wastewater in Hanoi is usually not treated and this untreated wastewater is directly discharged into one of the wastewater channels of the city and eventually reaches the ambient aquatic environment. The concentrations of the FQs, ciprofloxacin (CIP) and norfloxacin (NOR) in six hospital wastewaters ranged from 1.1 to 44 and from 0.9 to 17 micrgl(-1), respectively. Total FQ loads to the city sewage system varied from 0.3 to 14 g d(-1). Additionally, the mass flows of CIP and NOR were investigated in the aqueous compartment in a small wastewater treatment facility of one hospital. The results showed that the FQ removal from the wastewater stream was between 80 and 85%, probably due to sorption on sewage sludge. Simultaneously, the numbers of Escherichia coli (E. coli) were measured and their resistance against CIP and NOR was evaluated by determining the minimum inhibitory concentration. Biological treatment lead to a 100-fold reduction in the number of E. coli but still more than a thousand E. coli colonies per 100ml of wastewater effluent reached the receiving water. The highest resistance was found in E. coli strains of raw wastewater and the lowest in isolates of treated wastewater effluent. Thus, wastewater treatment is an efficient barrier to decrease the residual FQ levels and the number of resistant bacteria entering ambient waters. Due to the lack of municipal wastewater treatment plants, the onsite treatment of hospital wastewater before discharging into municipal sewers should be considered as a viable option and consequently implemented.