Challenges in understanding the sources of bioaccumulated metals in biota inhabiting turbid river systems

Bioaccumulation of As, Cd, Cu, Pb and Zn by Macrobrachium prawns was observed to occur in the Strickland River downstream of a gold mine at Porgera, Papua New Guinea. This was despite the total metal concentrations of waters and sediments indicating no difference from reference sites within tributaries. To provide information on potential sources and bioavailability of metals to prawns, an extensive range of analyses were made on waters, suspended solids, deposited sediments and plant materials within the river system. Dissolved metal concentrations were mostly sub-micrograms per liter and no major differences existed in concentrations or speciation between sites within the Strickland River or its tributaries. Similarly, no differences were detected between sites for total or dilute acid-extractable metal concentrations in bed sediments and plant materials, which may be ingested by the prawns. However, the rivers in this region are highly turbid and the dilute acid-extractable cadmium and zinc concentrations in suspended solids were greater at sites in the Strickland River than at sites in tributaries. The results indicated that mine-derived inputs increased the proportion of these forms of metals or metalloids in the Strickland River. These less strongly bound metals and metalloids would be more bioavailable to the prawns via the dietary pathway. The results highlighted many of the difficulties in using routine monitoring data without information on metal speciation to describe metal uptake and predict potential effects when concentrations are low and similar to background. The study indicated that the monitoring of contaminant concentrations in organisms that integrate the exposure from multiple exposure routes and durations may often be more effective for detecting impacts than intermittent monitoring of contaminants in waters and sediments.     

BIOCHEM-ORCHESTRA: a tool for evaluating chemical speciation and ecotoxicological impacts of heavy metals on river flood plain systems

The chemical speciation model BIOCHEM was extended with ecotoxicological transfer functions for uptake of metals (As, Cd, Cu, Ni, Pb, and Zn) by plants and soil invertebrates. It was coupled to the object-oriented framework ORCHESTRA to achieve a flexible and dynamic decision support system (DSS) to analyse natural or anthropogenic changes that occur in river systems. The DSS uses the chemical characteristics of soils and sediments as input, and calculates speciation and subsequent uptake by biota at various scenarios. Biotic transfer functions were field-validated, and actual hydrological conditions were derived from long-term monitoring data. The DSS was tested for several scenarios that occur in the Meuse catchment areas, such as flooding and sedimentation of riverine sediments on flood plains. Risks are expressed in terms of changes in chemical mobility, and uptake by flood plain key species (flora and fauna).     

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.     

Effects of salinity, DOM and metals on the fate and microbial toxicology of propetamphos formulations in river and estuarine sediment

Toxicity studies tend to use pure pesticides with single organisms. However, natural systems are complex and biological communities diverse. The organophosphate pesticide propetamphos (PPT) has been found exceeding regulatory limits (100 ng L⁻¹) in rivers. We address whether solution properties affect the fate of Analar (Analar-PPT) or industrial PPT (PPT-Ind) propetamphos formulations and whether propetamphos and metal toxicant effects are additive, antagonistic or synergistic? The sorption, desorption, biodegradation and microbial toxicology of Analar-PPT and PPT-Ind were investigated in Conwy River and estuary sediment. Results showed elevated salinity enhanced PPT sorption, while higher salinities increased PPT-Ind retention. Higher dissolved organic matter (DOM) and low salinity slowed Analar-PPT biodegradation (1.9 × 10⁻³ h⁻¹). Analar-PPT and PPT-Ind biodegradation was further reduced by low salinity, high DOM and dissolved Zn and Pb (6.3 × 10⁻⁴ h⁻¹, 1100 h t_½ for Analar-PPT; 7.5 × 10⁻⁴ h⁻¹, 924 h t_½ for PPT-Ind). Toxicity effects of PPT, Zn and Pb in equitoxic ratio were higher for PPT-Ind (4.7 μg PPT-Ind g⁻¹; 581 μg Zn g⁻¹; 395 μg Pb g⁻¹) than for Analar-PPT (34.6 μg PPT g⁻¹; 312 μg Zn g⁻¹; 212 μg Pb g⁻¹) whilst a toxicant ratio 1:100:10 suggested small quantities of Analar-PPT (EC₁₀ = 0.06 μg g⁻¹) affected microbial communities. The combined toxicity effect was more than additive. Thus, industrial formulations and pollutant mixtures should be considered when assessing environmental toxicity.     

Heavy metal content and speciation in groundwater of the Guadiamar river basin

This work presents the conclusions of a speciation study concerning Zn, Cd, Pb and Cu in groundwater from ten wells in the alluvial aquifers of the Guadiamar river, affected by Aznalcollar mine tailing spill (April 1998). The sampling campaign took place in January 2000, almost two years after the mining accident. Four metal fractions were determined: labile metal forms, H+ exchangeable metal forms, strongly inert forms (associated with organic and inorganic matter in solution), and forms associated with suspended matter. Total metal concentration in groundwater followed the trend Cd < Pb < Cu < Zn. The speciation study showed that Zn and Cd were present to a great extent in available forms (labile and H+ exchangeable), while Pb and Cu were found mostly in the less available forms (strongly inert). These results can illustrate the potential value of the speciation tool for the follow-up of spill-induced pollution in the area.     

Occurrence and fate of heavy metals in the wastewater treatment process

The occurrence and the fate of heavy metals (Cd, Pb, Mn, Cu, Zn, Fe and Ni) during the wastewater treatment process were investigated in the wastewater treatment plant (WTP) of the city of Thessaloniki, northern Greece, operating in the activated sludge mode. For this purpose, wastewater and sludge samples were collected from six different points of the plant, namely, the influent (raw wastewater, RW), the effluent of the primary sedimentation tank (primary sedimentation effluent, PSE), the effluent of the secondary sedimentation tank (secondary sedimentation effluent, SSE), sludge from the primary sedimentation tank (primary sludge, PS), activated sludge from the recirculation stream (activated sludge, AS), and the digested/dewatered sludge (final sludge, FS).

The distribution of metals between the aqueous and the solid phase of wastewater was investigated. Good exponential correlation was found between the metal partition coefficient, logK_p, and the suspended solids concentration. The mass balance of heavy metals in the primary, secondary and the whole treatment process showed good closures for all metal species. The relative distribution of individual heavy metals in the treated effluent and the sludge streams indicated that Mn and Cu are primarily (>70%) accumulated in the sludge, while 47–63% of Cd, Cr, Pb, Fe, Ni and Zn remain in the treated effluent.     

Influence of bacteria on Pb and Zn speciation, mobility and bioavailability in soil: A laboratory study

A soil column experiment was carried out to investigate the effects of inoculation of bacteria on metal bioavailability, mobility and potential leachability through single chemical extraction, consequential extraction and in situ soil solution extraction technologies. Results showed that bacteria inoculated, including Azotobacter chroococcum, Bacillus megaterium and Bacillus mucilaginosus, may pose both positive and negative impacts on bioavailability and mobility of heavy metals in soil, depending on the chemical nature of the metals. The activities of bacteria led to an increase of water dissolved organic carbon (DOC) concentration and a decrease of pH value, which enhanced metal mobility and bioavailability (e.g. an increase of water-soluble and HOAc-soluble Zn). On the other hand, bacteria could immobilize metals (e.g. a great reduction of water-soluble Pb) due to the adsorption by bacterial cell walls and possible sedimentation reactions with phosphate or other anions produced through bacterial metabolism.     

Release of hexachlorocyclohexanes from historically and freshly contaminated soils in China: implications for fate and regulation

Hexachlorocyclohexanes (HCHs) were produced and used in large quantity worldwide and are common soil pollutants. In this study, desorption of α-HCH and γ-HCH from two soil samples collected from a historical pesticide plant in Tianjin, China, was examined. As a comparison, desorption of freshly sorbed γ-HCH was examined, using five typical Chinese soils. Strong resistant desorption was observed for both historically contaminated and freshly contaminated soils, and desorption results were well modeled with a biphasic desorption isotherm. The unique thermodynamic characteristics associated with the desorption-resistant fraction indicated that physical constraint within soil organic matrices was likely the predominant mechanism controlling resistant desorption. Resistant desorption could have significant effects on fate and exposure of HCHs in soil environment. More accurate biphasic desorption models that take into account of the resistant desorption can be used to facilitate regulating, management and remediation of HCH-contaminated sites.     

Occurrence of toxic metals and their selective pressure for antibiotic-resistant clinically relevant bacteria and antibiotic-resistant genes in river receiving systems under tropical conditions

Environmental Science and Pollution Research - The co-occurrence of heavy metals, antibiotic-resistant bacteria (ARB) and antibiotic-resistance genes (ARGs) from hospital effluents spreading into...     

Environmental fate and bioavailability of agent orange and its associated dioxin during the vietnam war

BACKGROUND: In 1996, the Committee on the Assessment of Wartime Exposure to Herbicides in Vietnam of the National Academy of Sciences' Institute of Medicine (IOM) issued a report on an exposure model for use in epidemiological studies of Vietnam veterans. This exposure model would consider troop locations based on military records; aerial spray mission data; estimated ground spraying activity; estimated exposure opportunity factors; military indications for herbicide use; and considerations of the composition and environmental fate of herbicides, including changes in the TCDD content of the herbicides over time, the persistence of TCDD and herbicides in the environment, and the degree of likely penetration of the herbicides into the ground. When the final report of the IOM Committee was released in October 2003, several components of the exposure model envisioned by the Committee were not addressed. These components included the environmental fate of the herbicides, including changes in the TCDD content over time, the persistence of TCDD and herbicides in the environment, and the degree of likely penetration of herbicides into the ground. This paper is intended to help investigators understand better the fate and transport of herbicides and TCDD from spray missions, particularly in performing epidemiological studies. METHODS: This paper reviews the published scientific literature related to the environmental fate of Agent Orange and the contaminant, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), and discusses how this affected the potential exposure to TCDD of ground troops in Vietnam. Specifically, the mechanisms of dissipation and degradation as they relate to environmental distribution and bioavailability are addressed. RESULTS: The evaluation of the spray systems used to disseminate herbicides in Vietnam showed that they were capable of highly precise applications both in terms of concentrations sprayed and area treated. Research on tropical forest canopies with leaf area indices (a measure of foliage density) from 2 to 5 indicated that the amount of herbicide and associated TCDD reaching the forest floor would have been between 1 and 6% of the total aerial spray. Studies of the properties of plant surface waxes of the cuticle layer suggested that Agent Orange, including the TCDD, would have dried (i.e., be absorbed into the wax layer of the plant cuticle) upon spraying within minutes and could not be physically dislodged. Studies of Agent Orange and the associated TCDD on both leaf and soil surface have demonstrated that photolysis by sunlight would have rapidly decreased the concentration of TCDD, and this process continued in shade. Studies of 'dislodgeable foliar residues' (DFR, the fraction of a substance that is available for cutaneous uptake from the plant leaves) showed that only 8% of the DFR was present 1 hr after application. This dropped to 1% of the total 24 hrs after application. Studies with human volunteers confirmed that after 2 hrs of saturated contact with bare skin, only 0.15-0.46% of 2,4,5-T, one of the phenoxy acetic acid compounds that was an active ingredient of Agent Orange, entered the body and was eliminated in the urine. CONCLUSIONS: The prospect of exposure to TCDD from Agent Orange in ground troops in Vietnam seems unlikely in light of the environmental dissipation of TCDD, little bioavailability, and the properties of the herbicides and circumstances of application that occurred. Photochemical degradation of TCDD and limited bioavailability of any residual TCDD present in soil or on vegetation suggest that dioxin concentrations in ground troops who served in Vietnam would have been small and indistinguishable from background levels even if they had been in recently treated areas. Laboratory and field data reported in the literature provide compelling evidence on the fate and dislodgeability of herbicide and TCDD in the environment. This evidence of the environmental fate and poor bioavailability of TCDD from Agent Orange is consistent with the observation of little or no exposure in the veterans who served in Vietnam. Appreciable accumulation of TCDD in veterans would have required repeated long-term direct skin contact of the type experienced by United States (US) Air Force RANCH HAND and US Army Chemical Corps personnel who handled or otherwise had direct contact with liquid herbicide, not from incidental exposure under field conditions where Agent Orange had been sprayed.     

Distribution and fate of metals in the dispersion plume of a major municipal effluent

The environmental impacts of municipal wastewater discharges on receiving waters are numerous and inputs of contaminants such as metals can cause toxicity to organisms in receiving waters. The effluents generated by the treatment plant of the city of Montreal, Canada, the largest such facility in the St. Lawrence Valley, was investigated to determine the environmental fate of trace metals in the receiving waters. Total and extractable metal concentrations were determined and physico-chemical parameters were measured to characterize the receiving waters and evaluate their influence on the fate and behaviour of metals released from the urban effluent. Our results showed that particulate metals near the effluent discharge point are highly reactive and their distribution seems to be significantly influenced by the abundance of HCl-reactive iron and manganese, which act as trace-metal carriers. The partitioning of metals between dissolved and particulate phases varies along the effluent dispersion plume and therefore could strongly influence the exposure routes for aquatic organisms that are exposed to the various contaminants released from the effluent.     

Modeling the photo-oxidation of dissolved organic matter by ultraviolet radiation in freshwater lakes: implications for mercury bioavailability

Uncertainties in projected ultraviolet (UV) radiation may lead to future increases in UV irradiation of freshwater lakes. Because dissolved organic carbon (DOC) is the main binding phase for mercury (Hg) in freshwater lakes, an increase in DOC photo-oxidation may affect Hg speciation and bioavailability. We quantified the effect of DOC concentration on the rate of abiotic DOC photo-oxidation for five lakes (DOC=3.27-12.3 mg L(-1)) in Kejimkujik National Park, Canada. Samples were irradiated with UV-A or UV-B radiation over a 72-h period. UV-B radiation was found to be 2.36 times more efficient at photo-oxidizing DOC than UV-A, with energy-normalized rates of dissolved inorganic carbon (DIC) production ranging from 3.8×10(-5) to 1.1×10(-4) mg L(-1)J(-1) for UV-A, and from 6.0×10(-5) to 3.1×10(-4) mg L(-1)J(-1) for UV-B. Energy normalized rates of DIC production were positively correlated with DOC concentrations. Diffuse integrated attenuation coefficients were quantified in situ (UV-A K(d)=0.056-0.180 J cm(-1); UV-B K(d)=0.015-0.165 J cm(-1)) and a quantitative depth-integrated model for yearly DIC photo-production in each lake was developed. The model predicts that, UV-A produces between 3.2 and 100 times more DIC (1521-2851 mg m(-2) year(-1)) than UV-B radiation (29.17-746.7 mg m(-2) year(-1)). Future increases in UV radiation may increase DIC production and increase Hg bioavailability in low DOC lakes to a greater extent than in high DOC lakes.     

Green manure plants for remediation of soils polluted by metals and metalloids: Ecotoxicity and human bioavailability assessment

Borage, white mustard and phacelia, green manure plants currently used in agriculture to improve soil properties were cultivated for 10 wk on various polluted soils with metal(loid) concentrations representative of urban brownfields or polluted kitchen gardens. Metal(loid) bioavailability and ecotoxicity were measured in relation to soil characteristics before and after treatment. All the plants efficiently grow on the various polluted soils. But borage and mustard only are able to modify the soil characteristics and metal(loid) impact: soil respiration increased while ecotoxicity, bioaccessible lead and total metal(loid) quantities in soils can be decreased respectively by phytostabilization and phytoextraction mechanisms. These two plants could therefore be used for urban polluted soil refunctionalization. However, plant efficiency to improve soil quality strongly depends on soil characteristics.     

Increased bioavailability of metals in two contrasting agricultural soils treated with waste wood-derived biochar and ash

Recycled waste wood is being increasingly used for energy production; however, organic and metal contaminants in by-products produced from the combustion/pyrolysis residue may pose a significant environmental risk if they are disposed of to land. Here we conducted a study to evaluate if highly polluted biochar (from pyrolysis) and ash (from incineration) derived from Cu-based preservative-treated wood led to different metal (e.g., Cu, As, Ni, Cd, Pb, and Zn) bioavailability and accumulation in sunflower (Helianthus annuus L.). In a pot experiment, biochar at a common rate of 2 % w/w, corresponding to ～50 t ha^?1, and an equivalent pre-combustion dose of wood ash (0.2 % w/w) were added to a Eutric Cambisol (pH 6.02) and a Haplic Podzol (pH 4.95), respectively. Both amendments initially raised soil pH, although this effect was relatively short-term, with pH returning close to the unamended control within about 7 weeks. The addition of both amendments resulted in an exceedance of soil Cu statutory limit, together with a significant increase of Cu and plant nutrient (e.g., K) bioavailability. The metal-sorbing capacity of the biochar, and the temporary increase in soil pH caused by adding the ash and biochar were insufficient to offset the amount of free metal released into solution. Sunflower plants were negatively affected by the addition of metal-treated wood-derived biochar and led to elevated concentration of metals in plant tissue, and reduced above- and below-ground biomass, while sunflower did not grow at all in the Haplic Podzol. Biochar and ash derived from wood treated with Cu-based preservatives can lead to extremely high Cu concentrations in soil and negatively affect plant growth. Identifying sources of contaminated wood in waste stream feedstocks is crucial before large-scale application of biochar or wood ash to soil is considered.     

Comparison of a rhizosphere-based method with other one-step extraction methods for assessing the bioavailability of soil metals to wheat

There is no method recognized as a universal approach for evaluation of bioavailability of heavy metals in soil. Based on the simulation of the rhizosphere soil conditions and integration of the combined effects of root-soil interactions as a whole, a rhizosphere-based method has been proposed. Wet fresh rhizosphere soil was extracted by low-molecular-weight organic acids (LMWOAs) to fractionate metal fractions of soil pools, which were then correlated with the metal contents of wheat roots and shoots. The rhizosphere-based method was compared with other one-step extraction methods using DTPA, EDTA, CaCl2, and NaNO3 as extractants and the first step of the Community Bureau of Reference (BCR) method. Simple correlation and stepwise multiple regression analysis were used for the comparison. Simple correlation indicated that the extractable Cu, Zn, Cr, and Cd of soils by the rhizosphere-based method were significantly correlated with the metal contents of wheat roots. For DTPA, BCR1 and EDTA methods there was a relatively poor correlation between the extractable Cu, Zn and Cd of soil and metal contents of wheat roots. Stepwise multiple regression analysis revealed that the equation of the rhizosphere-based method was the simplest one, and no soil properties variables needed to be added. In contrast, the equations of other one-step extraction methods were more complicated, and soil properties variables needed to be entered. The most distinct feature of the rhizosphere-based method was that the recommended method was suitable for acidic, neutral and near alkaline soils. However, the DTPA and EDTA extraction methods were suitable for calcareous soils only-or-only for acidic soils. The CaCl2, and NaNO3 extraction methods were only suitable for exchangeable metals. In short, the rhizosphere-based method was the most robust approach for evaluation of bioavailability of heavy metals in soils to wheat.     

Changes in speciation and leaching behaviors of heavy metals in dredged sediment solidified/stabilized with various materials

Solidification/stabilization (S/S) of sediments is frequently used to treat contaminants in dredged sediments. In this study, sediment collected from the Pearl River Delta (China) was solidified/stabilized with three different kinds of functional materials: cement, lime and bentonite. Lime primarily acted via induced increases in pH, while cements stabilization occurred through their silicate-based systems and the main function of bentonite was adsorption. The speciation and leaching behaviors of specific heavy metals before and after S/S were analyzed and the results showed that the residual speciation of Cd, Cr, Ni, Pb and Zn increased in all treatments except for Cu, as the exchangeable speciation, carbonate-bound speciation and Fe-Mn-oxide-bound speciation of Cu (all of which could be stabilized) were less than 2 % of the total amount. Pb leaching only decreased when pH increased, while the mobility of Cr and Ni only decreased in response to the silicate-based systems. The leached portion of the Fe-Mn-oxide-bound speciation followed the order Zn?>?Cu?>?Ni/Cd?>?Pb?>?Cr. The leached portion of organic-matter-bound species was less than 4 % for Cd, Cr, Ni and Pb, but 35.1 % and 20.6 % for Cu and Zn, respectively.     

Octanol-solubility of dissolved and particulate trace metals in contaminated rivers: implications for metal reactivity and availability

The lipid-like, amphiphilic solvent, n-octanol, has been used to determine a hydrophobic fraction of dissolved and particulate trace metals (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) in contaminated rivers. In a sample from the River Clyde, southwest Scotland, octanol-solubility was detected for all dissolved metals except Co, with conditional octanol-water partition coefficients, D(ow), ranging from about 0.2 (Al and Cu) to 1.25 (Pb). In a sample taken from the River Mersey, northwest England, octanol-solubility was detected for dissolved Al and Pb, but only after sample aliquots had been spiked with individual ionic metal standards and equilibrated. Spiking of the River Clyde sample revealed competition among different metals for hydrophobic ligands. Metal displacement from hydrophobic complexes was generally most significant following the addition of ionic Al or Pb, although the addition of either of these metals had little effect on the octanol-solubility of the other. In both river water samples hydrophobic metals were detected on the suspended particles retained by filtration following their extraction in n-octanol. In general, particulate Cu and Zn (up to 40%) were most available, and Al, Co and Pb most resistant (<1%) to octanol extraction. Distribution coefficients defining the concentration ratio of octanol-soluble particle-bound metal to octanol-soluble dissolved metal were in the range 10(3.3)-10(5.3)mlg(-1). The presence of hydrophobic dissolved and particulate metal species has implications for our understanding of the biogeochemical behaviour of metals in aquatic environments. Specifically, such species are predicted to exhibit characteristics of non-polar organic contaminants, including the potential to penetrate the lipid bilayer. Current strategies for assessing the bioavailability and toxicity of dissolved and particulate trace metals in natural waters may, therefore, require revision.     

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.     

Toxicity of combined sewer overflows on river phytoplankton: the role of heavy metals

The toxic effect of a combined sewer overflow (CSO) on the phytoplankton community of the river Seine has been studied by means of short-term primary production measurements. As the discharged solids usually do not remain in the water column, only filtered or centrifugated fractions were tested. The collected phytoplankton were grown in the laboratory for 2 days, after addition of N, P and EDTA. Stock cultures in exponential growth were directly tested with heavy metals, but resuspended algal cells were used for effluent testing. The results show an increase of EC50 value for the single metal species in the order Cu相似文献