Toxicity of imidacloprid to the terrestrial isopod Porcellio scaber (Isopoda, Crustacea)

Imidacloprid is a neonicotinoid insecticide with neurotoxic action that, as a possible alternative for commonly used organophosphorus pesticides, has gained registration in about 120 countries for use in over 140 agricultural crops. Only few data are available on its toxicity for soil invertebrates. We therefore assessed the effects of imidacloprid on survival, weight gain, feeding rate, total protein content, glutathione S-transferase activity (GST), and digestive gland epithelial thickness in juveniles and adults of the terrestrial isopod Porcellio scaber. After two weeks of feeding on imidacloprid-dosed food, weight gain (NOEC 5 microg/g dry food) and feeding rate (NOEC 10 microg/g) in juveniles, and feeding rate (NOEC<10 microg/g) and digestive gland epithelial thickness (NOEC<10 microg/g) in adults were most affected. In juveniles induction of GST activity and increase of total protein content per wet animal weight was detected at 5 microg/g dry food, whereas in adults a reduction of GST was observed at 25 microg/g (NOEC 10 microg/g). An estimate of actual intake rates suggests that imidacloprid affects isopods at similar exposure concentrations as insects. The toxicity of imidacloprid was similar to that of the organophosphorus pesticide diazinon, tested earlier using the same methods [Stanek, K., Drobne, D., Trebse, P., 2006. Linkage of biomarkers along levels of biological complexity in juvenile and adult diazinon fed terrestrial isopod (Porcellio scaber, Isopoda, Crustacea). Chemosphere 64, 1745-1752]. At actual environmental concentrations, diazinon poses a higher risk to P. scaber. Due to its increasing use in crop protection and higher persistence in soil, imidacloprid might however, be potentially more dangerous after long-term application. We conclude that toxicity testing with P. scaber provides relevant, repeatable, reproducible and comparable toxicity data that is useful for the risk assessment of pesticides in the terrestrial environment.     

Reduced survival and body size in the terrestrial isopod Porcellio scaber from a metal-polluted environment

Terrestrial isopods (woodlice) may show trade-offs in life history parameters when exposed to toxins. We have shown previously [Jones and Hopkin (1996) Functional Ecology 10, 741-750] that woodlice which survive to reproduce in sites heavily polluted with metals from an industrial smelting works do not alter their reproductive allocation. This study investigates whether there are differences in the survival and body size of Porcellio scaber from these same populations. Specimens were collected from eight sites at different distances from the Avonmouth smelter, UK. The sites represented a gradient of concentrations of Zn, Cd, Pb and Cu in the woodlice, from background levels to a grossly contaminated sites close to the smelter. In laboratory trials, the number of days survived by starved males showed a significant decline with increased concentrations of Zn in those animals. The maximum size of both sexes declined significantly from the least to the most polluted sites. The most polluted sites had significantly fewer large animals. The cost of detoxifying assimilated metals appears to be reduced energy reserves and smaller body size.     

Long-term Hg pollution induced Hg tolerance in the terrestrial isopod Porcellio scaber (Isopoda, Crustacea)

The aim of our work was to assess the pollution-induced community tolerance (PICT) of isopod gut microbiota and pollution-induced isopod population tolerance (PIPT). Animals collected from a chronically Hg polluted and an unpolluted location were exposed for 14 days to 10microg Hg/g dry food under laboratory conditions. The lysosomal membrane stability, hepatopancreas epithelium thickness, feeding activity and animal bacterial gut microbiota composition were determined. The results confirm the hypothesis that the response to short-term Hg exposure differs for animals from the Hg polluted and the unpolluted field locations. The animals and their gut microbiota from the Hg polluted location were less affected by Hg in a short-term feeding experiment than those from the unpolluted environment. We discuss the pollution-induced population tolerance of isopods and their gut microbiota as a measure of effects of long-term environmental pollution. The ecological consequences of such phenomena are also discussed.     

Linkage of biomarkers along levels of biological complexity in juvenile and adult diazinon fed terrestrial isopod (Porcellio scaber, Isopoda, Crustacea)

In parallel laboratory experiments, we determined the effect of a typical representative of organophosphorous pesticides, diazinon, on AChE activity, lipid, protein and glycogen content, weight change, feeding activity and mortality of juvenile and adult terrestrial isopods Porcellio scaber (Isopoda, Crustacea). Organophosphorous pesticides (OP) are among the most extensively used pesticides, which have replaced organochlorine pesticides. OPs inhibit the enzyme acetylcholinesterase (AChE), resulting in neurotoxicity. They have more widespread effects on non-target organisms than do organochlorine pesticides. The aim of this study was to link effect of diazinon on target enzyme to energy reserves and to integrated biomarker responses in juvenile and adult P. scaber. The non-observed effect concentration (NOEC) for AChE activity after diazinon exposure in two weeks toxicity study with isopods was below 5 microg/g diazinon. There was a good agreement between concentrations at which AChE and survival were affected (10 microg/g diazinon in juveniles, 100 microg/g diazinon in adults). We revealed a link among AChE activity, protein content and mortality. Glycogen and lipid content, feeding activity and weight change were not affected in two weeks diazinon exposure up to 100 microg/g diazinon. Juveniles were affected at concentrations that were an order of magnitude lower than those provoking similar effects on adults. Recommendations are made for future toxicity studies with terrestrial isopods.     

Lac Dufault sediment core trace metal distribution, bioavailability and toxicity to Hyalella azteca

To determine changes in metal distribution, bioavailability and toxicity with sediment depth, two 20-cm-long replicate cores were collected from a lake historically subjected to the influence of metal mining and smelting activity. The vertical distribution of Pb, Cd and Cu in sediment was similar for all three metals, with the surface layers showing enrichment and the deeper (pre-industrial) layers showing lower concentrations. Toxicity of each sediment core section was determined in laboratory tests with the freshwater amphipod Hyalella azteca. Bioavailable metal in each sediment slice was estimated from metal concentrations in overlying water in these toxicity tests and, for Cd, also from metal bioaccumulation. The profile for Cd in tissue was comparable to Cd in sediment and overlying water, but relative Cd bioavailability from sediment increased with sediment depth. Survival increased with increasing sediment depth, suggesting that surface sediments were probably less or non-toxic before industrialization.     

重金属镉对污水生物膜吸附菲的影响机制

为了探究重金属镉(Cd)对污水生物膜吸附菲(phenanthrene,PHE)的影响及机制,以新疆乌鲁木齐某含油污水库生物膜为研究对象,通过对比有Cd²⁺和无Cd²⁺条件下,污水生物膜对PHE的吸附性能,Cd²⁺的存在对污水生物膜吸附PHE有促进作用。有Cd²⁺和无Cd²⁺条件下,在pH=6、温度为35 ℃时污水生物膜对PHE的吸附效果最好;吸附动力学和吸附等温线方程均符合拟二级动力学和Langmuir模型,说明吸附以单分子层的化学吸附为主,并且有Cd²⁺时污水生物膜对PHE的最大吸附量比无Cd²⁺时高出21.8%。SEM、FTIR和XPS的表征分析结果表明,有Cd²⁺和无Cd²⁺条件下污水生物膜表面与PHE发生作用的基团基本相同,吸附过程中的主要官能团为有机质中的羟基、羧基和酰胺基团。     

白云石和硫酸亚铁复配对城市污泥中重金属形态分布及生物有效性的影响

以合肥市某污水处理厂污泥为研究对象,研究白云石、硫酸亚铁以及白云石和硫酸亚铁复合物作为改良剂对污泥重金属形态和生物有效性的影响,并对其钝化机理进行了初步研究。结果表明:白云石可以提高污泥pH,硫酸亚铁则降低污泥的pH,白云石和硫酸亚铁复配添加时,污泥pH变化并不显著。白云石对污泥中Cu和Cd有较好钝化作用,硫酸亚铁对污泥中As具有显著钝化作用,白云石和铁盐复配对污泥中重金属Cu、Zn、Cd和As均有显著钝化作用。白云石和硫酸亚铁处理可显著降低污泥中重金属有效态含量,其中以5%白云石和5%硫酸亚铁复配处理的效果最好,与对照相比,污泥中的有效Cu、Zn、Cd和As分别减少了59.58%、42.26%、40.93%和55.68%。SEM-EDS和Visual MINTEQ模拟结果显示,白云石中的碳酸根离子能够与重金属发生沉淀反应。盆栽实验结果显示,污泥中加入白云石和硫酸亚铁后,青菜地上部和根部重金属含量降低,地上部Cu、Zn、Cd和As最大降低程度分别为53.56%、34.51%、57.29和77.04%。     

土壤铜形态和生物有效性对施用生物质炭的响应

采用改进的Tessier方法对土壤Cu形态进行分级,研究了添加生物质炭对土壤重金属Cu形态、生物有效性和小麦生长及生理指标的影响。结果表明,石灰性土壤中Cu主要以碳酸盐结合态、氧化态和残渣态形式存在,三者占土壤Cu的90%以上。添加生物质炭后,土壤中的碳酸盐结合态铜、氧化态铜含量有所减少,但不显著;有机物结合态铜含量增加了131.25%,达到极显著水平,其中主要增加了紧有机结合态。添加生物质炭在培养一定时间后（30 d后）土壤有效态铜含量降低,120天时最大降低幅度达50.66%,添加生物质炭提高了冬小麦的根系重、茎秆干重、籽粒干重和灌浆期旗叶叶绿素含量,降低了根系、茎秆和籽粒的含铜量以及超氧化物歧化酶（SOD）活性,并随着生物质炭施用量的增加有显著性差异。综合看来,生物质炭对土壤铜污染具有钝化作用。     

Evaluation of surrogate measures of cadmium, lead, and zinc bioavailability to Eisenia fetida

We evaluated weak-electrolyte (0.1 M Ca(NO3)2) soil extractions and ion-exchange membranes coated with a metal chelator as measures of Cd, Pb, and Zn bioavailability in spiked artificial soil by comparing their metal availability estimates to acute lethal toxicity in the earthworm Eisenia fetida. Ca(NO3)2 extractions were precisely related to toxicity in all toxicity tests, and enabled the development of time-independent LC50S (incipient lethal-levels, ILLs) calculated using exposure levels based on extraction data. ILLs with 95% CIs for the Cd, Pb, and Zn toxicity tests were 9.8 (9.4-10.3), 1.16 (1.11-1.22), and 6.33 (6.18-6.49) Ca(NO3)2-extractable mmol metal/kg soil, respectively. Mixture toxicity of Cd, Pb, and Zn, assessed using the toxic unit (TU) approach, was 1.35 TU, suggesting additivity. Chelating ion-exchange membrane uptake was variable, and not well related to toxicity. Weak-electrolyte extractions show promise as precise, inexpensive surrogate measures of Cd, Pb, and Zn bioavailability in soil.     

Effect of new soil metal immobilizing agents on metal toxicity to terrestrial invertebrates

Application of 5% (w:w) novel metal immobilizing agent reduced the water soluble, the calcium chloride extracted as well as the pore water concentration of zinc in soils from Maatheide, a metal contaminated site in the northeast of Belgium. Addition of the metal immobilizing agents also eliminated acute toxicity to the potworm Enchytraeus albidus and the earthworm Eisenia fetida and chronic toxicity to the springtail Folsomia candida. Cocoon production by E. fetida, however, was still adversely affected. These differences may be explained by the species dependent routes of metal uptake: F. candida is probably mainly exposed via pore water while in E. fetida dietary exposure is probably also important. From these results it is clear that organisms with different exposure routes should be used simultaneously to assess the environmental risk of metal contaminated soils.     

Influence of titanium dioxide nanoparticles on speciation and bioavailability of arsenite

In this study, the influence of the co-existence of TiO₂ nanoparticles on the speciation of arsenite [As(III)] was studied by observing its adsorption and valence changing. Moreover, the influence of TiO₂ nanoparticles on the bioavailability of As(III) was examined by bioaccumulation test using carp (Cyprinus carpio). The results showed that TiO₂ nanoparticles have a significant adsorption capacity for As (III). Equilibrium was established within 30 min, with about 30% of the initial As (III) being adsorbed onto TiO₂ nanoparticles. Most of aqueous As (III) was oxidized to As(V) in the presence of TiO₂ nanoparticles under sunlight. The carp accumulated considerably more As in the presence of TiO₂ nanoparticles than in the absence of TiO₂ nanoparticles, and after 25-day exposure, As concentration in carp increased by 44%. Accumulation of As in viscera, gills and muscle of the carp was significantly enhanced by the presence of TiO₂ nanoparticles.     

Spatial distribution of acid-volatile sulphide concentration and metal bioavailability in mangrove sediments from the Brisbane River, Australia

Acid-volatile sulphide (AVS) was measured at regular positions along eight transects through a mangrove forest in the Brisbane River, Queensland, Australia. Concentrations ranged from 0.33 to 22.61 micromol S g(-1) sediment dry weight. There was no correlation between AVS concentration and the proportion of clay-sand in the sediment, but sediments with high AVS concentrations tended to contain more water (rs=0.43; p=0.01). AVS concentrations were used to assess the potential bioavailability of the sediment heavy metal burden. The spatial variability of potential bioavailability was high and depended to a great extent on which metals were considered as part of the AVS complexing system. It is suggested seasonal variations would further increase the observed variability in bioavailability. This variation should be taken into account when monitoring and assessing long-term trends in sediment toxicity.     

Interactions between copper and cadmium modify metal organ distribution in mature tilapia, Oreochromis mossambicus

Sexually mature female tilapia were exposed to sublethal concentrations of waterborne Cu and/or Cd over 6 days, and subsequent body concentrations of these metals were determined in several organs. The results show that the distribution of Cu and Cd was metal and organ specific. This is demonstrated, for example, by the observation that in tilapia, Cu exposure did not result in Cu accumulation in the liver, whereas in the intestinal wall, notably high concentrations of Cu and Cd were measured in metal exposed fish. In addition to single metal exposed fish, we also determined Cu and Cd body distribution in Cu?Cd co-exposed fish. The observed interactions in metal accumulation were most pronounced in the organs of fish exposed to low, environmentally realistic, metal concentrations.     

The influence of pH on cadmium toxicity to the green alga Stichococcus bacillaris and on the cadmium forms present in the culture medium

Cadmium toxicity to the green alga Stichococcus bacillaris was investigated in media of pH 3-9. A significant decrease of cadmium toxicity occurred in both the acidic and alkaline ranges of pH. In media of pH 3 and 9, cadmium did not affect the dry mass content substantially. Maximum toxicity of cadmium was noticed at pH 6-7. Voltametric investigations showed a significant effect of pH on electrochemically measured cadmium content in the culture media. Hydrolysis of the medium components and formation of cadmium complexes with OH(-) ions caused a considerable decrease in amounts of electrochemically measured cadmium in the alkaline range of pH.     

Recombinant luminescent bacterial sensors for the measurement of bioavailability of cadmium and lead in soils polluted by metal smelters

Environmental hazard of heavy metals in soils depends to a large extent on their bioavailability. The approach used in this study enables the determination of bioavailable metals in solid-phase samples. Two recombinant bacterial sensors, one responding specifically to cadmium and the other to lead and cadmium by increase of luminescence (firefly luciferase was used as a reporter) were used to determine the bioavailability of these metals in soil-water suspensions (a contact assay) and respective particle-free extracts. Fifty agricultural soils sampled near zinc and lead smelters in the Northern France containing up to (mg/kg) 20.1 of Cd, 1050 of Pb and 1390 of Zn were analysed. As the soil matrix interferes with the assay, recombinant luminescent control bacteria lacking the metal recognizing protein and corresponding promoter (thus, being not metal-inducible) but otherwise comparable to the sensor bacteria (the same host bacterium and plasmid encoding luciferase) were used in parallel to take into account the possible quenching and/or stimulating effects of the sample on the luminescence of the sensor bacteria. Both, chemical and sensor analysis showed that only microg/l levels of metals were extracted from the soil into the water phase (0.1% of the total Cd, 0.07% of Pb and 0.5% of Zn). However, 115-fold more Cd and 40-fold more Pb proved bioavailable if the sensor bacteria were incubated in soil suspensions (i.e., in the contact assay). The bioavailability of metals in different soils varied (depending probably on soil type) ranging from 0.5% to 56% for cadmium and from 0.2% to 8.6% for lead.     

The effects of aging time on the fraction distribution and bioavailability of PAH

Understanding the effects of aging time on the fraction distribution and bioavailability of PAH, such as phenanthrene (PHE) and pyrene (PYR), has considerable benefits for risk assessment, food security and remediation strategies for contaminated soil. The results of the present study show that the proportion of the desorbed PHE decreased from ca. 82% at day 0 to ca. 65% at day 150. In addition, non-desorbed PHE increased from ca. 18% at day 0 to ca. 31% at day 150, whereas the changes of desorbed and non-desorbed PYR showed no significant trend during this aging period. The proportion of desorbed PYR was lower than that of PHE, whereas the opposite occurred with the non-desorbed fraction. After 150 d of aging, the proportion of bound residues (PHE and PYR) increased significantly with the cultivating time from ca. 0.2% to ca. 4.7% and ca. 0.1% to ca. 1.2% for PHE and PYR, respectively. In addition, the bioavailability of PAH (PHE and PYR) to earthworms was also assessed over 0-150 d. The results showed that the uptake rate and bioconcentration factor (BCF) of pollutants by earthworms displayed the following biphasic character: a rapid decrease over the first 15 d followed by a slow decrease over the next 135 d. Moreover, the earthworm uptake rate of PHE was greater than that of PYR throughout the incubation period, indicating that PHE has a higher bioavailability than PYR. In addition, the positive correlation between the uptake rate of earthworms and PAH extractability suggested that a three-step extraction is a reliable approach to predict PHE bioavailability in soil. However, a limit was observed for PYR.     

Effects of sediment composition on inorganic mercury partitioning, speciation and bioavailability in oxic surficial sediments

Artificially prepared sediments were used to assess the effects of sediment composition on inorganic Hg partitioning, speciation and bioavailability. Organic coating in sediment greatly increased the Hg partitioning and the amount of bioavailable Hg bound with the clay and the Fe and Mn oxides, but had little effect on that bound with the quartz and calcium carbonate as a result of weaker binding of humic acids and fulvic acids. The clay content increased the concentration of Hg in the sediments but inhibited the gut juice extraction due to the strong binding of Hg-organic matter (OM) complexes. Most Hg in the sediments was complexed by OM (mainly distributed in the organo-complexed phase and the strongly complexed phase), and the Hg-OM complexes (especially Hg in the strongly complexed phase) in sediments contributed much to gut juice extraction. Redistribution of Hg-OM complexes between sediments and gut juices may occur during gut juice extraction and modify Hg bioavailability and speciation in sediments.     

Runoff rates,chemical speciation and bioavailability of copper released from naturally patinated copper

The release of copper, induced by atmospheric corrosion, from naturally patinated copper of varying age (0 and 30 years) has been investigated together with its potential ecotoxic effect. Results were generated in an interdisciplinary research effort in which corrosion science and ecotoxicology aspects were combined. The aim of the investigation was to elucidate the situation when copper-containing rainwater leaves a roof in terms of runoff rate, chemical speciation, bioavailability and ecotoxicity effects. Data have been collected during a three-year field exposure conducted in the urban environment of Stockholm, Sweden. The potential environmental effects have been evaluated using a combination of a copper specific biosensor test with the bacterium Alcaligenes eutrophus and the conventional 72-h growth inhibition test with the green alga Raphidocelis subcapitata. The results show annual runoff rates between 1.0 and 1.5 g/m2 year for naturally patinated copper of varying age. The runoff rate increased slightly with patina age, which mainly is attributed to the enhanced first flush effect observed on thicker patina layers. The total copper concentration in investigated runoff samplings ranged from 0.9 to 9.7 mg/l. Both computer modeling and experimental studies revealed that the majority (60-100%) of released copper was present as the free hydrated cupric ion, Cu(H2O)6(2+), the most bioavailable copper species. However, other copper species in the runoff water, such as, e.g. Cu(OH)+ and Cu2(OH)2(2+), were also bioavailable. The copper-containing runoff water, sampled directly after release from the roof, caused significant reduction in growth rate of the green alga. It should be emphasized that the results describe the runoff situation immediately after release from the copper roof and not the real environmental ecotoxicity. Therefore the data should only be used as an initial assessment of the potential environmental effect of copper runoff from building applications. Future risk assessments should also consider dilution effects of copper, changes in its chemical speciation and bioavailability during environmental entry, and type and sensitivity of the receiving ecosystem.     

The effects of chemical remediation treatments on the extractability and speciation of cadmium and lead in contaminated soils

Two rural soils contaminated by cadmium (Cd) and lead (Pb) were used to evaluate the effect of different chemical treatments on changes in speciation and extractability of Cd and Pb, and in phytoavailability to wheat. Triplicates of seven chemical treatments were tested to compare and evaluate the remediation techniques for contaminated soils using pot experiments. Treatments applied were calcium carbonate, a high quantity of phosphate salt, hog composts, iron oxide, manganese oxide, zeolite, and unamended control. Wheat (Triticum aestivum) was planted in the different amended soils for a further one month to evaluate the effectiveness of treatments on uptake of Cd and Pb by the wheat shoots. Results indicated that addition of calcium carbonate, manganese oxide, or zeolite reduces the extractability of Cd or Pb in both soils, and significantly reduce the uptake of Cd and Pb by wheat shoots. Changes in the extractability and metal sequential fractionations indicate that the exchangeable (or available) form of Cd and Pb in two soils can be transformed into unavailable forms after these amendments.