底泥生长基质中重金属的迁移特征及生物有效性

河道底泥中重金属含量较高,重金属的迁移性及生物有效性是限制疏浚底泥土地施用或用作废弃场地修复基质资源化利用途径的主要因素。以沈阳细河待疏浚底泥为材料,通过盆栽实验的方法研究了河道底泥与碱性粉煤灰、炉渣和锯木屑配比基质中重金属在紫花苜蓿体内累积、迁移及生物有效性的变化。结果发现,配比底泥基质上紫花苜蓿生物量、株高及株径均好于纯底泥处理,其中底泥、粉煤灰、炉渣、锯木屑以2：0．5：0．5：0．5配比的s2处理中紫花苜蓿生物量是纯底泥处理的11．7倍。与底泥对照相比,配比底泥基质上植株体内重金属含量极显著降低,而且地上部重金属含量显著低于根部含量;底泥基质中紫花苜蓿地上部和根部对Cd、Cu、Pb、Zn的富集系数（BCF）显著低于底泥处理,但转移系数（TF）无显著变化,富集系数（BCF）和转移系数（TF）均小于1．0。紫花苜蓿种植后底泥基质中重金属含量显著低于农用污泥重金属控制标准,除Cd含量略高外,Cu、Pb和Zn含量低于土壤环境质量三级标准。这些结果表明,城市重污染河道底泥经过合理处置后,重金属浓度、活性及生物有效性降低,在其土地施用或废弃地修复中可以用作一些耐性植物的生长基质。     

Effect of spatial variation on salinity tolerance of macroinvertebrates in Eastern Australia and implications for ecosystem protection trigger values

Salinisation of freshwater has been identified as a serious environmental issue in Australia and around the world. Protective concentrations (trigger values) for salinity can be used to manage salinity impacts, though require locally relevant salinity tolerance information. 72-h acute salinity tolerance values were determined for 102 macroinvertebrates collected from 11 locations in four biologically distinct freshwater bio-regions in Northeast Australia and compared with sensitivities observed in Southeast Australia. The salinity tolerance of individual taxa was consistent across Northeast Australia and between Northeast and Southeast Australia. However, two distinct communities were identified in Northeast Australia using distributions of the acute tolerance values and a calculated index of salinity sensitivity. Salinity trigger values should therefore be representative of local or regionally relevant communities and may be adequately calculated using sensitivity values from throughout Eastern Australia. The results presented provide a basis for assessing salinity risk and determining trigger values for salinity in freshwater ecosystems at local and regional scales in Eastern Australia.     

Trends in the occurrence of human and veterinary antibiotics in the sediments of the Yellow River, Hai River and Liao River in northern China

The occurrence of four classes of 17 commonly used antibiotics (including fluoroquinolones, tetracycline, sulfonamides, and macrolides) was investigated in the sediments of the Yellow River, Hai River and Liao River in northern China by using rapid resolution liquid chromatography-tandem mass spectrometry. Higher concentrations were detected for most antibiotics in the sediments of the Hai River than in the sediments of the other rivers. Norfloxacin, ofloxacin, ciprofloxacin and oxytetracycline in the three rivers were most frequently detected with concentrations up to 5770, 1290, 653 and 652 ng/g, respectively. High frequencies and concentrations of the detected antibiotics were often found in the downstream of large cities and areas influenced by feedlot and fish ponds. Good fitted linear regression equations between antibiotic concentration and sediment physicochemical properties (TOC, texture and pH) were also found, indicating that sediment properties are important factors influencing the distribution of antibiotics in the sediment of rivers.     

Impact of the earthworm Lumbricus terrestris (L.) on As, Cu, Pb and Zn mobility and speciation in contaminated soils

To assess the risks that contaminated soils pose to the environment properly a greater understanding of how soil biota influence the mobility of metal(loid)s in soils is required. Lumbricus terrestris L. were incubated in three soils contaminated with As, Cu, Pb and Zn. The concentration and speciation of metal(loid)s in pore waters and the mobility and partitioning in casts were compared with earthworm-free soil. Generally the concentrations of water extractable metal(loid)s in earthworm casts were greater than in earthworm-free soil. The impact of the earthworms on concentration and speciation in pore waters was soil and metal specific and could be explained either by earthworm induced changes in soil pH or soluble organic carbon. The mobilisation of metal(loid)s in the environment by earthworm activity may allow for leaching or uptake into biota.     

Roles of pyrolysis on availability,species and distribution of Cu and Zn in the swine manure: Chemical extractions and high-energy synchrotron analyses

Animal manures generally contain high levels of heavy metals that may pose a significant threat to soil and groundwater qualities. Pyrolysis as means of reducing metal availability in such feed stocks is recently encouraged, but systematic studies are currently lacking. The aim of this study was to assess the impact of pyrolysis temperature on the availability of Cu and Zn by chemical extraction, to determine the speciation of Cu and Zn by synchrotron-based X-ray spectroscopy, and finally to investigate the phase distribution of metal species in the carbonaceous materials by combining acid–base extractions and absorption spectroscopy data. The results showed that both Cu and Zn in the swine manure were mainly bound to organic functional groups. Cu (II) reduction and Cu (I)–S complexes were observed during the pyrolysis process. Zn species resembling ZnAc₂ was still dominant, being 60.8–69.2%, and ZnS increased by 6.6–21.8% in the carbonaceous materials. The distribution of Cu and Zn in the mineral, carbonized and non-carbonized organic phases varied greatly with the pyrolysis temperature. The higher the temperature, the more the metals existed in the mineral phase and carbonized organic phase. The decrease of EDTA extractable Cu and Zn with pyrolysis temperature was due to the increase of metals in the carbonized organic phase and mineral phase. It is suggested that pyrolysis at the relatively higher temperature is a better choice for metal-containing manure according to the metal speciation, solubility and availability.     

Use of whole-body and subcellular Cu residues of Lumbriculus variegatus to predict waterborne Cu toxicity to both L. variegatus and Chironomus riparius in fresh water

We tested the use of whole-body and subcellular Cu residues (biologically-active (BAM) and inactive compartments (BIM)), of the oligochaete Lumbriculus variegatus to predict Cu toxicity in fresh water. The critical whole-body residue associated with 50% mortality (CBR₅₀) was constant (38.2-55.6 μg g⁻¹ fresh wt.) across water hardness (38-117 mg L⁻¹ as CaCO₃) and exposure times during the chronic exposure. The critical subcellular residue (CSR₅₀) in metal-rich granules (part of BIM) associated with 50% mortality was approximately 5 μg g⁻¹ fresh wt., indicating that Cu bioavailability is correlated with toxicity:subcellular residue is a better predictor of Cu toxicity than whole-body residue. There was a strong correlation between the whole-body residue of L. variegatus (biomonitor) and survival of Chironomus riparius (relatively sensitive species) in a hard water Cu co-exposure. The CBR₅₀ in L. variegatus for predicting mortality of C. riparius was 29.1-45.7 μg g⁻¹ fresh wt., which was consistent within the experimental period; therefore use of Cu residue in an accumulator species to predict bioavailability of Cu to a sensitive species is a promising approach.     

Measurements of Cd, Cu, Pb and Zn in the lower reaches of major Eurasian arctic rivers using trace metal clean techniques

Concentrations of dissolved and particulate Cd, Cu, Pb and Zn were determined in samples collected in summer 1998 from the lower reaches of six major Eurasian arctic rivers: the Onega, Severnaya Dvina, Mezen, Pechora, Ob and Yenisey. These data comprise some of the earliest measurements of trace metals in Eurasian arctic rivers above the estuaries using recognized clean techniques. Significant (α = 0.05) differences were observed among mean concentrations of particulate metals in the individual rivers (F ≤ 0.006), with highest levels overall observed in the Severnaya Dvina and Yenisey. No significant differences were observed among mean concentrations of dissolved metals in the individual rivers (F = 0.10-0.84). Contributions from anthropogenic sources are suggested by comparison of trace metal ratios in the samples to crustal abundances. These results establish a baseline for assessing future responses of Eurasian arctic river systems to climate-related environmental changes and shifting patterns of pollutant discharge.     

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.     

Kinetic extractions to assess mobilization of Zn, Pb, Cu, and Cd in a metal-contaminated soil: EDTA vs. citrate

Kinetic EDTA and citrate extractions were used to mimic metal mobilization in a soil contaminated by metallurgical fallout. Modeling of metal removal rates vs. time distinguished two metal pools: readily labile (QM1) and less labile (QM2). In citrate extractions, total extractability (QM1+QM2) of Zn and Cd was proportionally higher than for Pb and Cu. Proportions of Pb and Cu extracted with EDTA were three times higher than when using citrate. We observed similar QM1/QM2 ratios for Zn and Cu regardless of the extractant, suggesting comparable binding energies to soil constituents. However, for Pb and Cd, more heterogeneous binding energies were hypothesized to explain different kinetic extraction behaviors. Proportions of citrate-labile metals were found consistent with their short-term, in-situ mobility assessed in the studied soil, i.e., metal amount released in the soil solution or extracted by cultivated plants. Kinetic EDTA extractions were hypothesized to be more predictive for long-term metal migration with depth.     

Effect of salinity and sediment characteristics on the sorption and desorption of perfluorooctane sulfonate at sediment-water interface

This study investigated the influence of solution salinity, pH and the sediment characteristics on the sorption and desorption of perfluorooctane sulfonate (PFOS). The results showed that the sorption of PFOS onto sediment increased by a factor of 3 as the CaCl₂ concentration increased from 0.005 to 0.5 mol L⁻¹ at pH 7.0, and nearly 6 at pH 8.0. Desorption hysteresis occurred over all salinity. The thermodynamic index of irreversibility (TII) values increased with increasing concentration of CaCl₂. Maximum irreversibility was found in the sorption systems with CaCl₂ in the concentration of 0.5 mol L⁻¹. The results suggested that PFOS can be largely removed from the water with increasing salinity, and get trapped onto sediments irreversibly. These phenomena could be explained by salting-out effect and Ca-bridging effect. Studies also suggested that the content of total organic carbon is the dominant psychochemical properties of sediment controlling the sorption of PFOS.     

Occurrence and distribution of sediment-associated insecticides in urban waterways in the Pearl River Delta, China

Sediment-associated pesticides, including organochlorine (OCP), organophosphate (OP), and pyrethroid insecticides, were analyzed in urban waterways in three cities (Guangzhou, Dongguan, and Shenzhen) in the Pearl River Delta (PRD), China. The OCPs represented 27.2% of the detectable insecticides in sediment, and chlordanes, DDTs, and endosulfans were the most frequently detected OCPs. The currently used insecticide chlorpyrifos was the only OP detected above the reporting limit (RL), with concentrations ranging from <RL to 100 ng g⁻¹ dry weight (dw). Additionally, pyrethroids were detected in all sediments with the sum pyrethroid concentrations ranging from 4.26 to 384 ng g⁻¹ dw and this represented 64.9% of the sum insecticide concentration. Despite their widespread use, no studies have been conducted investigating the occurrence and distribution of pyrethroids in China. As the first report of pyrethroids in urban waterways in China, the current study found cypermethrin was the most abundant insecticide detected in the PRD at concentrations ranging from 1.44 to 219 ng g⁻¹ dw. Spatially, sediment from more populous and urbanized areas (Shenzhen and Tianhe district in Guangzhou) had higher insecticide residues than less populous agricultural areas. In the more modernized city of Shenzhen, the OCPs were seldom detected, whereas more diverse patterns of pyrethroids were observed. Potential sources of these insecticides, especially the frequently detected pyrethroids, were most likely from pest control during urban landscaping maintenance and from abatement programs targeting mosquitoes and ants. Results suggested that a shift in application pattern and elevated urbanization increased accumulation of currently used insecticides like pyrethroids in sediment, and made them the predominate insecticides in the PRD urban waterways.     

Combined effects of deltamethrin, temperature and salinity on oxidative stress biomarkers and acetylcholinesterase activity in the black tiger shrimp (Penaeus monodon)

This study aimed to investigate the interactions of two abiotic factors (temperature and salinity) and deltamethrin (pyrethroid pesticide) exposure on some oxidative stress biomarkers as well as on acetylcholinesterase activity (AChE) in hepatopancreas, gills and muscle of black tiger shrimp (Penaeus monodon). A combination of three temperatures (24, 29 and 34 °C), two salinities (15 and 25 ppt), and the absence or presence of 0.1 μg L⁻¹ deltamethrin was applied on shrimp during 4 d under laboratory conditions. Lipid peroxidation level (LPO) and glutathione S-transferase activity (GST) were not affected by combined effect of temperature, salinity and deltamethrin in any of the studied tissues. Deltamethrin impaired other tested oxidative stress biomarkers, i.e. total glutathione (tGSH), catalase (CAT), glutathione peroxidase (GPx). tGSH level significantly increased in hepatopancreas due to deltamethrin exposure mainly at 34 °C, while pesticide effects on tGSH and CAT activity in gills were influenced by both temperature and salinity. In addition, GPx activity in hepatopancreas decreased after deltamethrin treatment mainly at 24 °C. Finally, AChE in muscle was strongly inhibited by deltamethrin at all tested temperatures and salinities. These novel findings demonstrate that interactions between abiotic factors and a commonly used pesticide exposure should be taken into account when analyzing some widespread biomarkers in black tiger shrimp.     

Geographical and pedological drivers of distribution and risks to soil fauna of seven metals (Cd, Cu, Cr, Ni, Pb, V and Zn) in British soils

Concentrations of seven metals were measured in over 1000 samples as part of an integrated survey. Sixteen metal pairs were significantly positively correlated. Cluster analysis identified two clusters. Metals from the largest (Cr, Cu, Ni, V, Zn), but not the smallest (Cd, Pb) cluster were significantly negatively correlated with spatial location and soil pH and organic matter content. Cd and Pb were not correlated with these parameters, due possibly to the masking effect of recent extensive release. Analysis of trends with soil properties in different habitats indicated that general trends may not necessarily be applicable to all areas. A risk assessment indicated that Zn poses the most widespread direct risk to soil fauna and Cd the least. Any risks associated with high metal concentrations are, however, likely to be greatest in habitats such as arable and horticultural, improved grassland and built up areas where soil metal concentrations are more frequently elevated.     

Content, distribution and fate of 33 elements in sediments of rivers receiving wastewater in Hanoi, Vietnam

Untreated industrial and domestic wastewater from Hanoi city is discharged into rivers that supply water for various agricultural and aqua-cultural food production systems. The aim of this study was to assess the content, distribution and fate of 33 elements in the sediment and pore water of the main wastewater receiving rivers. The sediment was polluted with potentially toxic elements (PTEs) with maximum concentrations of 73 As, 427 Cd, 281 Cr, 240 Cu, 218 Ni, 363 Pb, 12.5 Sb and 1240 Zn mg kg(-1) d.w. Observed distribution coefficients (log(10) K(d,obs)) were calculated as the ratio between sediment (mg kg(-1) d.w.) and pore water (mg L(-1)) concentrations. Maxima log(10) K(d,obs) were >4.26 Cd, >6.60 Cu, 4.78 Ni, 7.01 Pb and 6.62 Zn. The high values show a strong PTE retention and indicate the importance of both sorption and precipitation as retention mechanisms. Sulphide precipitation was a likely mechanism due to highly reduced conditions.     

Trace metals assessment in water, sediment, mussel and seagrass species--validation of the use of Posidonia oceanica as a metal biomonitor

The accumulation of trace metals (Cd, Co, Cr, Hg, Ni and Pb) was measured in water, sediment, the mussel Mytilus galloprovincialis and the seagrass Posidonia oceanica. Samples were collected in three locations of the north-western Mediterranean (Canari, Livorno and Porto-Torres) which present different levels and sources of human impact. Analyses in the different compartments (water, sediment, M. galloprovincialis and P. oceanica) have allowed to identify Canari as the most Cd, Co, Cr and Ni contaminated site; Livorno as the most Hg contaminated and Porto-Torres as the most Pb contaminated. Furthermore, for the first time, metal concentrations found in P. oceanica have been compared with those found in the water column, in the sediment and in the recognized metal bio-indicator species M. galloprovincialis and the results obtained have led to the same conclusions. Thus, this study allows to validate the use of P. oceanica as metal biomonitor of coastal waters.     

Metal and metalloid removal in constructed wetlands, with emphasis on the importance of plants and standardized measurements: A review

This review integrates knowledge on the removal of metals and metalloids from contaminated waters in constructed wetlands and offers insight into future R&D priorities. Metal removal processes in wetlands are described. Based on 21 papers, the roles and impacts on efficiency of plants in constructed wetlands are discussed. The effects of plant ecotypes and class (monocots, dicots) and of system size on metal removal are addressed. Metal removal rates in wetlands depend on the type of element (Hg > Mn > Fe = Cd > Pb = Cr > Zn = Cu > Al > Ni > As), their ionic forms, substrate conditions, season, and plant species. Standardized procedures and data are lacking for efficiently comparing properties of plants and substrates. We propose a new index, the relative treatment efficiency index (RTEI), to quantify treatment impacts on metal removal in constructed wetlands. Further research is needed on key components, such as effects of differences in plant ecotypes and microbial communities, in order to enhance metal removal efficiency.     

Spatial distribution and vertical profile of polybrominated diphenyl ethers, tetrabromobisphenol A, and decabromodiphenylethane in river sediment from an industrialized region of South China

Polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A (TBBPA), and decabromodiphenylethane (DBDPE) were detected in fifteen surface sediments and two sediment cores collected from a river in one heavily industrialized region of South China. TBBPA and DBDPE were detected with concentrations ranging from 3.8 to 230 ng/g dw and from 23 to 430 ng/g dw, respectively. Σtri-hepta-BDEs and Σnona-deca-BDEs ranged from 0.7 to 7.6 ng/g dw and from 30 to 5700 ng/g dw, respectively. Σtri-hepta-BDEs showed an increasing trend whereas for Σnona-deca-BDE two sediment cores revealed a decreasing trend in more recent sediment layers which may attributed to the introduction of DBDPE. The rapid increasing trend for TBBPA and DBDPE in recent sediment layers well reflected the rising demand of these two compounds in study area.     

Interaction effects of salinity,sewage sludge,and earthworms on the fractionations of Zn and Cu,and the metals uptake by the earthworms in a Zn- and Cu-contaminated calcareous soil

Environmental Science and Pollution Research - This study assessed the effects of salinity and sewage sludge on the fractionation of Zn and Cu in a soil around a lead-zinc mine as well as their...     

Effect of biosolid incorporation to mollisol soils on Cr, Cu, Ni, Pb, and Zn fractionation, and relationship with their bioavailability

Biosolid application to soil may be a supply of nutrients and micronutrients but it may also accumulate toxic compounds which would be absorbed by crops and through them be incorporated to the trophic chain.

The present study deals with the effect of biosolid application on Cr, Cu, Pb, Ni, and Zn in agricultural soils. The procedure used is sequential extraction so that the availability of those metals may be estimated and related to their bioavailability as determined through two indicator plants grown in greenhouse: ryegrass (Lolium perenne L.) and red clover (Trifolium pratense). Results showed that biosolid application to soil increased total Cu and Zn content. Sequential extraction showed that the more labile Zn fractions increased after biosolid application to soil. This was confirmed when assessing the total content of this metal in shoot and root of the plants under study, since a higher content was found in plant tissues, while no significant differences were found for Cu, Cr, Ni, and Pb.     

Ecological risk assessment of heavy metals in sediment and human health risk assessment of heavy metals in fishes in the middle and lower reaches of the Yangtze River basin

The concentrations of heavy metals (Cr, Cd, Hg, Cu, Zn, Pb and As) in the water, sediment, and fish were investigated in the middle and lower reaches of the Yangtze River, China. Potential ecological risk analysis of sediment heavy metal concentrations indicated that six sites in the middle reach, half of the sites in the lower reach, and two sites in lakes, posed moderate or considerable ecological risk. Health risk analysis of individual heavy metals in fish tissue indicated safe levels for the general population and for fisherman but, in combination, there was a possible risk in terms of total target hazard quotients. Correlation analysis and PCA found that heavy metals (Hg, Cd, Pb, Cr, Cu, and Zn) may be mainly derived from metal processing, electroplating industries, industrial wastewater, and domestic sewage. Hg may also originate from coal combustion. Significant positive correlations between TN and As were observed.