Bioaccumulation and toxicity of a cationic surfactant (DODMAC) in sediment dwelling freshwater invertebrates

Dimethyldioctadecylammonium chloride (DODMAC, CAS No. 107-64-2) is the principal active component of Di(hydrogenated tallow alkyl) dimethylammonium chloride (DHTDMAC, CAS No. 61789-80-8), a cationic surfactant formerly used principally in laundry fabric softeners. After discharge to water, DODMAC partitions strongly to sediment, therefore the assessment of the effects of DODMAC to benthic organisms is essential in any risk assessment. Chronic toxicity studies were conducted with Lumbriculus variegatus (Oligochaete), Tubifex tubifex (Oligochaete) and Caenorhabditis elegans (Nematode). NOECs were greater than 5738, 1515 and 1351 mg/kg dw, respectively, even for sub-lethal effects. Measurement of the route of uptake of DODMAC by L. variegatus demonstrated the relative importance of uptake via ingestion (86%) compared with direct contact with the sediment and via pore water (14%). The overall tendency of DODMAC to bioaccumulate, however, was low with measured accumulation factors of 0.22 and 0.78 for L. variegatus and T. tubifex, respectively.     

Bioaccumulation of heavy metals in the earthworms Lumbricus rubellus and Aporrectodea caliginosa in relation to total and available metal concentrations in field soils

The aim of this study was to determine important metal pools for bioaccumulation by the earthworms Lumbricus rubellus and Aporrectodea caliginosa in soils with high binding capacity. Cd, Cu and Zn concentrations in soil, pore water and CaCl(2) extracts of soil, in leaves of the plant species Urtica dioica and in earthworms were determined at 15 field sites constituting a gradient in metal pollution. Variations in the Cu and Cd concentrations in L. rubellus and Cu concentrations in A. caliginosa were best explained by total soil concentrations, while variation in Cd concentration in A. caliginosa was best explained by pore water concentrations. Zn concentrations in L. rubellus and A. caliginosa were not significantly correlated to any determined variable. It is concluded that despite low availability, earthworms in floodplain soils contain elevated concentrations of Cu and Cd, suggesting that uptake takes place not only from the soluble metal concentrations.     

Effects of heavy metals on sea urchin embryo development. Part 2. Interactive toxic effects of heavy metals in synthetic mine effluents

Interactive toxic effects between heavy metals were investigated using a sea urchin (Anthocidaris crassispina) bioassay. An effluent from an abandoned mine showed significant inhibitory effects on embryo development as well as producing specific malformations. The effects on the embryos were reproduced by synthetic polluted seawater consisting of eight metals (manganese, lead, cadmium, nickel, zinc, chromium, iron, and copper) at the concentrations detected in the mine effluent. This indicated that the heavy metals were responsible for the effects observed. Five heavy metals were ranked in decreasing order of toxicity as follows: Cu>Zn>Pb>Fe>Mn. Among these, zinc and manganese could cause malformation of the embryos. From bioassay results using 27 combinations of heavy metals, 16 combinations including zinc could produce specific malformations, such as radialized, exo-gastrulal, and spaceship Apollo-like gastrulal embryos. Zinc was one of the elements responsible for causing malformations and its effects were intensified by the presence of the other metals, such as manganese, lead, iron, and copper.     

Bioaccumulation kinetics of sediment-associated DE-83 in benthic invertebrates (Nereis succinea, polychaete)

Polychaetes (Nereis succinea) were exposed to DE-83 contaminated sediments to investigate the bioaccumulation and bioavailability of nona- and deca-BDEs in sediment. All the major congeners in DE-83 were bioavailable to the lugworms. The uptake coefficients (K_s) of nona- and deca-BDE congeners in lugworms were in the range of 0.18-0.65 (d⁻¹), with the values of BDE-207 and -208 slightly higher than those of BDE-206 and -209. Elimination of nona- and deca-BDE congeners from lugworms was very fast. The estimated half-lives of nona- and deca-BDE congeners in the lugworms were at 0.7 d. The bioavailability of nona- and deca-BDE congeners was very low, with BSAF of 0.017 for BDE-206 and -209 and 0.054 for BDE-207 and -208. These may be due to the large molecular size and high affinity of PBDEs to sediment particles. The contribution of BDE-206 in the profile of nona-BDEs in lugworm tissue decreased with exposure time while those of BDE-207 and -208 increased, which could be the result of the biotransformation of BDE-209 to BDE-207 and -208.     

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.     

Taiwan's industrial heavy metal pollution threatens terrestrial biota

The bioconcentration levels of essential (Cu, Fe, Mg, Mn, and Zn) and non-essential (As, Cd, Hg, Pb, and Sn) elements have been investigated in different terrestrial biota such as fungi, plant, earthworm, snail, crab, insect, amphibian, lizard, snake, and bat including the associated soil, to investigate the ecosystem health status in Kenting National Park, Taiwan. High bioconcentrations of Cd, Hg, and Sn in snail, earthworm, crab, lizard, snake, and bat indicated a contaminated terrestrial ecosystem. High concentrations of Cd, Hg, and Sn in plant species, effective bioaccumulation of Cd by earthworm, snail, crab and bat, as well as very high levels of Hg found in invertebrates, amphibians, and reptiles revealed a strong influence from industrial pollution on the biotic community. This study for the first time presents data on the impact of heavy metal pollution on various terrestrial organisms in Taiwan.     

Interspecific variation in heavy metal body concentrations in Hong Kong marine invertebrates

Accumulated body concentrations of cadmium, copper and zinc were investigated in 19 species of intertidal invertebrates (the barnacles Tetraclita squamosa, Capitulum mitella, Balanus amphitrite, Megabalanus volcano, the bivalves Saccostrea cucullata, Septifer virgatus and Brachidontes atratus, the chiton Acanthopleura japonica and the gastropods Cellana grata, Cellana toreuma, Patelloida saccharina, Patelloida pygmaea, Siphonaria japonica, Tegula argyrostoma, Lunella coronata, Monodonta labio, Nerita albicilla, Thais clavigera and Thais luteostoma) collected from a relatively unpolluted area in Hong Kong, i.e. two shores within the Cape d'Aguilar Marine Reserve. In general body metal concentrations could be explained by the accumulation strategy of the analysed organism and by physiological requirements for the essential metals, i.e. copper and zinc. Zinc concentrations were, therefore, greatest in the barnacles and the oyster S. cucullata. Copper concentrations were greatest in those gastropods containing the respiratory pigment haemocyanin and in S. cucullata. One species collected from the sheltered shore, i.e. T. luteostoma, had much higher copper body concentrations compared with exposed shore conspecifics and this may be attributed to a diet that was dominated by oysters, which have high copper body concentrations. In contrast to both copper and zinc, cadmium body concentrations showed little interspecific variation.     

污泥中重金属的去除及回收试验

论述了利用离子交换技术循环使用柠檬酸去除污泥中重金属,并置换回收重金属的适宜工艺条件.经柠檬酸处理后,污泥中90%以上的重金属被去除;柠檬酸处理液中的重金属用离子交换法回收,考察了树脂种类、流速、操作方式等因素对离子交换、再生效果的影响;在适宜工艺条件下,重金属的交换率均为100%,而洗脱率均接近90%;柠檬酸及离子交换树脂循环使用,重金属也得到回收,降低了处理成本.     

Salinity increases mobility of heavy metals in soils

The effect of salinity induced by CaCl₂, MgCl₂, NaCl and Na₂SO₄ on the mobility of Cu, Cd, Pb and Zn was studied. An increase of ionic strength by any salts promoted a higher release of Cd than the others metals. When CaCl₂ and NaCl were applied, Cd and Pb showed the highest degree of mobilization. When MgCl₂ was applied, Cd and Cu were mobilized the most. Finally, an increase of Na₂SO₄ also promoted the strongest mobilization of Cd and Cu.As the total heavy metal content was higher, the percentage of Pb and Cu released upon salinization decreased, indicating that these metals are strongly bound to soil constituents. An increase of carbonates in the soil promoted a higher release of Pb for all used salts and for Zn when MgCl₂ and NaCl were used. This indicates that Pb and Zn are adsorbed on the surface of carbonate crystals. An increase of fine particles promoted a decrease of percentage of released Cd for all salts, indicating that Cd is strongly retained in the fine fractions.The main mechanism regulating Pb and Cd mobility was competition with Ca²⁺ for sorption sites followed for metal chloro-complexation, association between the Cd/Pb-sulfates and competition with Mg²⁺. The main mechanism regulating Cu mobility was the formation of Cu-sulfate, followed by competition with cations (Mg > Ca) and chloride. For Zn, competition with Ca²⁺ for sorption sites was the most important process for its mobility; followed by Zn-sulfate association and, finally, chloride and competition with Mg with the same effect.     

Bioaccumulation of metals and effects of a landfill in small mammals. Part II. The wood mouse, Apodemus sylvaticus

We assess the bioaccumulation of metals (Pb, Hg, Cd, Fe, Mg, Zn, Cu, Mn, Mo, Cr) and effects of landfill leachates on morphological (RI, relative weights), plasma (GPT, GOT, creatinine), and genotoxic (MNT) parameters in wood mice, Apodemus sylvaticus, inhabiting close the Garraf landfill site (NE Spain). Due to the high age- and sex-dependent variation in wild populations, we also studied the effect of these biotic factors on the parameters studied. Wood mice from the landfill site, sited in a partially protected area, showed more Cd, Fe, Zn, Cu, Mn, Mo, and Cr than specimens from the reference site. Moreover, mice near the landfill registered low RI and high relative renal weight, GPT, and MN frequency, which indicate that the landfill affects the health of wild mice. In contrast to sympatric shrews from a previous study, wood mice showed lower bioaccumulation of metals and lower variation caused by biotic factors. Moreover, the morphological and physiological alterations demonstrated that they were also more sensitive at environmental pollution. Given the contribution of small mammals to ecosystem function and the scarce ecotoxicological data on the effects of landfill pollution on wild terrestrial mammals, we consider that our study can be used to improve the management of this protected area.     

Enhanced removal of heavy metals in primary treatment using coagulation and flocculation.

The goal of this study was to determine the removal efficiencies of chromium, copper, lead, nickel, and zinc from raw wastewater by chemically enhanced primary treatment (CEPT) and to attain a total suspended solids removal goal of 80%. Operating parameters and chemical doses were optimized by bench-scale tests. Locally obtained raw wastewater samples were spiked with heavy metal solutions to obtain representative concentrations of metals in wastewater. Jar tests were conducted to compare the metals removal efficiencies of the chemical treatment options using ferric chloride, alum, and anionic polymer. The results obtained were compared with those from other studies. It was concluded that CEPT using ferric chloride and anionic polymer is more effective than CEPT using alum for metals removal. The CEPT dosing of 40 mg/L ferric chloride and 0.5 mg/L polymer enhanced heavy metals removal efficiencies by over 200% for chromium, copper, zinc, and nickel and 475% for lead, compared with traditional primary treatment. Efficient metals capture during CEPT can result in increased allowable headworks loadings or lower metal levels in the outfall.     

灯心草部分生理生化指标对土壤复合重金属胁迫的响应

通过盆栽试验,以叶绿素含量和POD、SOD、CAT3种抗氧化酶活性作为观测指标,研究了Cu、Cd、Pb、Zn和As复合重金属胁迫下灯心草部分生理生化指标的变化趋势和机理.结果表明,灯心草的生理毒害效应呈明显的剂量-效应关系.表现为与对照相比,叶绿素含量减少,叶绿素a/b值降低,叶片失绿现象明显.随着复合重金属胁迫浓度的增加,灯心草3种酶活性均呈先升后降的变化趋势,但出现抗性酶活性高峰所对应的重金属浓度不同,表现出不同的特征变化趋势.总体来说,在接近土壤环境质量标准低浓度设计范围内,酶活性有逐渐被激活的趋势.但在高浓度水平下,酶活性普遍受到抑制.生长在铅锌尾矿和模拟矿毒水污染土壤中的灯心草叶绿素合成受到显著抑制(P＜0.05),但POD和CAT两种酶活性均高于对照.     

Bioconcentration and biokinetics of heavy metals in the earthworm

This study examines the steady state and non-steady state kinetics of five metals, cadmium, copper, lead, nickel, and zinc in earthworms. The steady state kinetics are based on field studies in which worms from contaminated and uncontaminated sites were collected and measurements were made of concentrations in the earthworms and soils. For each of the metals, evidence suggests that bioconcentration depends on the metal concentrations in the soil; bioconcentration is greater at lower soil concentrations. The studies of non-steady state kinetics involve uptake and elimination experiments in which worms are transferred from an uncontaminated soil to a contaminated soil (uptake studies) or from a contaminated soil to an uncontaminated soil (elimination studies). The voiding time is shown to be an important experimental variable in determining the measured levels of metal in earthworms because experimental measurements are usually made on a worm-soil complex (i.e. the soft tissue of the worm and the soil in the gut of the worm). Thus, for metals that are bioconcentrated in worm tissue, increasing the voiding period increases the concentration of the metal in the worm-soil complex. Conversely, for metals that are not bioconcentrated, increasing the voiding time leads to a decrease in concentrations in the worm-soil complex.     

生活垃圾焚烧飞灰重金属的受热特性

研究了飞灰重金属在不同煅烧温度下的挥发情况及其存在形态.结果表明:重金属挥发能力由强到弱依次为Hg＞Pb＞As、Cd＞Zn＞Cr、Ni、Cu;其中Hg、Pb、As和Cd属易挥发重金属,在1 150 ℃时几乎全部挥发;Zn属较易挥发重金属,1 150 ℃时的挥发率在40%～50%;Cr、Ni和Cu属难挥发重金属,在1 150 ℃的挥发率不超过10%;在400～1 150 ℃,随温度的升高,部分Zn、Hg、Cu、Pb、Cd、Ni和As由可溶态向残渣态、铁锰氧化态转化;在400～900 ℃,随温度的升高Cr可溶态比例减少,而在900～1 150 ℃,随温度的升高其可溶态比例增加.     

Bioaccumulation of metals and effects of landfill pollution in small mammals. Part I. The greater white-toothed shrew, Crocidura russula

Here we quantified the bioaccumulation of metals (lead, mercury, cadmium, iron, magnesium, zinc, copper, manganese, molybdenum, and chromium) and assessed several morphological (RI, relative weights) and genotoxic parameters as biomarkers of pollution from the landfill of Garraf (Barcelona, NE Spain). Specimens of Crocidura russula (Insectivora, Mammalia) from the landfill site showed increased Pb, Cd, Mg, Zn, Cu, and Cr concentrations in their tissues. Levels of mercury were below detection limits. Concentrations of Cd, Pb, and Cr varied significantly with age and no differences were found between males and females. While no differences were found in morphological parameters between shrews from the two sites, those from the polluted one showed more micronuclei in blood than those from reference site (1.786+/-0.272 vs. 0.088+/-0.045 per thousand; U=46.000, p<0.001). The considerable amounts of potentially toxic metals (Pb till 59.71 and Cd till 56.57microgg(-1) DW in kidneys) and the genotoxic effects indicate the harmful effect on biota. We consider necessary biomonitoring this landfill sited in a partially protected area.     

Distribution of pesticides and heavy metals in trophic chain

Determination of triazines herbicides (atrazine and simazine) by high performance liquid chromatography (HPLC) in samples of trophic chain were worked out. Determination limits of 0.5 μg g⁻¹ for atrazine, 0.8 μg g⁻¹ for simazine with pesticides recovery of 70–77% in trophic chain samples were obtained. The content of simazine in soils was in range 1.72–57.89 μg g⁻¹, in grass 5–88 μg g⁻¹, in milk 2.32–15.29 μg g⁻¹, in cereals 10.98–387 μg g⁻¹, in eggs 30.14–59.48 μg g⁻¹, for fruits: 2.45–6.19 μg g⁻¹. The content of atrazine in soils was in range 0.69–19.59 μg g⁻¹, in grass 7.85–23.85 μg g⁻¹, in cereals 1.88–43.08 μg g⁻¹. Cadmium, lead and zinc were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) in the same samples as atrazine and simazine. Determination limits for cadmium 5 × 10⁻³ μg g⁻¹, for lead 1 × 10⁻² μg g⁻¹, and for zinc 0.2 × 10⁻³ μg g⁻¹, were obtained. The content of cadmium in soil was in range 0.13–5.89 μg g⁻¹, in grass 114–627.72 × 10⁻³ μg g⁻¹, in milk 8.88–61.88 × 10⁻³ μg g⁻¹, in cereals 0.20–0.31 μg g⁻¹, in eggs 0.11–0.15 μg g⁻¹, in fruits 0.23–0.59 μg g⁻¹. The content of lead in soils was in range 0.57–151.50 μg g⁻¹, in grass 0.16–136.57 μg g⁻¹, in milk 1.16–3.74 μg g⁻¹, in cereals 1.05–5.47 μg g⁻¹, in eggs 5.79–55.87 μg g⁻¹, in fruits 21.00–87.36 μg g⁻¹. Zinc content in soil was in range 9.15–424.5 μg g⁻¹, in grass 35.20–55.87 μg g⁻¹, in milk 20.00–34.38 μg g⁻¹, in cereals 14.94–28.78 μg g⁻¹, in eggs 15.67–32.01 μg g⁻¹, in fruits 14.94–18.88 μg g⁻¹.

Described below extraction and mineralization methods for particular trophic chains allowed to determine of atrazine, simazine, cadmium, lead and zinc with good repeatability and precision. Emphasis was focused on liquid–liquid extraction and solid-phase extraction of atrazine and simazine from analysed materials, as well as, on monitoring the content of herbicides and metals in soil and along trophic chain. Higher concentration of pesticides in samples from west region of Poland in comparison to that of east region is likely related to common applying them in Western Europe in relation to East Europe. The content of metals strongly depends on samples origin (industry area, vicinity of motorways).     

Seasonal bioavailability of sediment-associated heavy metals along the Mississippi river floodplain.

A value of simultaneously extracted metal to acid-volatile sulfide (SEM-AVS) can provide important information regarding metal availability in anaerobic sediment. SEM and AVS concentrations were obtained by the cold-acid purge-and-trap technique during spring and summer at six locations along the Mississippi River floodplain. SEM-AVS values and AVS concentrations did not vary significantly between locations during both seasons. AVS concentrations were significantly greater during summer than spring, resulting in significantly lower SEM-AVS values in summer. Total SEM concentrations did not significantly vary between seasons or specific locations. SEM-AVS values were greater than one at each location during both seasons. Sediment metal toxicity was predicted to be absent for benthic organisms along the river floodplain.     

Earthworm contamination by PCBs and heavy metals

A comparison is made of soil and earthworm contamination by PCBs and heavy metals between a nature reserve and two sites conditioned by the addition of sewage sludge and compost.The tissues and gut content of the earthworms shows a higher PCB concentration than that of the surrounding soil and also a difference in the fingerprint of some single PCB compounds.Earthworms display a selective accumulation of cadmium and zinc in their tissues and gut content.     

Road traffic emission factors for heavy metals

Quantifying the emissions and concentrations of heavy metals in urban air is a prerequisite for assessing their health effects. In this paper a combination of measurements and modelling is used to assess the contribution from road traffic emissions. Concentrations of particulate heavy metals in air were measured simultaneously during 1 year at a densely trafficked street and at an urban background site in Stockholm, Sweden. Annual mean concentrations of cadmium were 50 times lower than the EU directive and for nickel and arsenic concentrations were 10 and six times lower, respectively. More than a factor of two higher concentrations was in general observed at the street in comparison to roof levels indicating the strong influence from local road traffic emissions. The only compound with a significantly decreasing trend in the urban background was Pb with 9.1 ng m^?3 in 1995/96 compared to 3.4 ng m^?3 2003/04. This is likely due to decreased emissions from wear of brake linings and reduced emissions due to oil and coal combustion in central Europe.Total road traffic emission factors for heavy metals were estimated using parallel measurements of NOx concentrations and knowledge of NOx emission factors. In general, the emission factors for the street were higher than reported in road tunnel measurements. This could partly be due to different driving conditions, since especially for metals which are mainly emitted from brake wear, more stop and go driving in the street compared to in road tunnels is likely to increase emissions. Total emissions were compared with exhaust emissions, obtained from the COPERT model and brake wear emissions based on an earlier study in Stockholm. For Cu, Ni and Zn the sum of brake wear and exhaust emissions agreed very well with estimated total emission factors in this study. More than 90% of the road traffic emissions of Cu were due to brake wear. For Ni more than 80% is estimated to be due to exhaust emissions and for Zn around 40% of road traffic emissions are estimated to be due to exhaust emissions. Pb is also mainly due to exhaust emissions (90%); a fuel Pb content of only 0.5 mg L^?1 would give similar emission factor as that based on the concentration increment at the street. This is the first study using simultaneous measurements of heavy metals at street and roof enabling calculations of emission factors using a tracer technique.     

Irrigation of certain Mediterranean plants with heavy metals

The ability of some Mediterranean plant species to absorb heavy metals present in wastewater from treatment plants is researched. Their tolerance to high concentrations of heavy metals is also assessed. Myoporum sp., Nerium oleander and Geranium sp. were irrigated with wastewater, normal irrigation water, and irrigation water enriched with metals. The concentration of metals in the wastewater, irrigation water, in the soil, and in the leaves, tissues and roots of the plants were measured. The results show that treatment of plants with wastewater gives slightly increased concentrations of metals in leaves and roots. In contrast, irrigation with high concentrations of Cu₂₊, Mn₂₊ and Zn₂₊ (up to 1000 mg/1) resulted to significantly higher concentrations of these metals in the roots than in the leaves. However, all plants have been shown to tolerate high concentrations of heavy metals except Nerium oleander, which exhibited strong toxicity in leaves. The tolerance of these Mediterranean plant species to polluted environments allows them to be irrigated by wastewater from treatment plants, so as to achieve the best environmental rehabilitation of desertified Mediterranean areas.