A modified receptor model for source apportionment of heavy metal pollution in soil.

Source apportionment is a crucial step toward reduction of heavy metal pollution in soil. Existing methods are generally based on receptor models. However, overestimation or underestimation occurs when they are applied to heavy metal source apportionment in soil. Therefore, a modified model (PCA-MLRD) was developed, which is based on principal component analysis (PCA) and multiple linear regression with distance (MLRD). This model was applied to a case study conducted in a peri-urban area in southeast China where soils were contaminated by arsenic (As), cadmium (Cd), mercury (Hg) and lead (Pb). Compared with existing models, PCA-MLRD is able to identify specific sources and quantify the extent of influence for each emission. The zinc (Zn)-Pb mine was identified as the most important anthropogenic emission, which affected approximately half area for Pb and As accumulation, and approximately one third for Cd. Overall, the influence extent of the anthropogenic emissions decreased in the order of mine (3 km) > dyeing mill (2 km) ≈ industrial hub (2 km) > fluorescent factory (1.5 km) > road (0.5 km). Although algorithm still needs to improved, the PCA-MLRD model has the potential to become a useful tool for heavy metal source apportionment in soil.

Heavy metal pollution and health risk assessment of agricultural soils in a typical peri-urban area in southeast China.

Heavy metal pollution in peri-urban areas in China is serious and complex. We thus developed an integrated evaluation method to assess heavy metal pollution and potential health risk to residents in a typical peri-urban area with diverse anthropogenic emission sources and cropping systems. Ecological risk was evaluated using Nemerow's synthetical pollution index (Pn) and Potential ecological risk index (RI). Then polluted areas and responsible emission sources were identified by GIS mapping. Health risk caused by food intake and soil exposure was calculated by accounting for the influence of anthropogenic emissions and cropping systems. Agricultural soils in the study area were polluted by cadmium (Cd), mercury (Hg), lead (Pb), and arsenic (As). High concentrations mainly occurred near the mining area and along the roadsides. The accumulation of heavy metals in crops followed the order of tea leaves > rice grain > vegetables. The hazard index of potential human health risk caused by chronic soil exposure and food intake was 15.3, indicating obvious adverse health effects. 87.5% of health risk was attributed to food consumption, and significantly varied among different cropping systems with the decreasing order of rice (10.44) >vegetable (2.86) > tea (0.05). The integrated method of ecological and health risk index, which takes consideration of both anthropogenic emission and cropping system can provide a practical tool for evaluating of agricultural soil in the peri-urban area regrading different risk factors.

Anthropogenic mercury emissions from 1980 to 2012 in China.

China was considered the biggest contributor for airborne mercury in the world but the amount of mercury emission in effluents and solid wastes has not been documented. In this study, total national and regional mercury emission to the environment via exhaust gases, effluents and solid wastes were accounted with updated emission factors and the amount of goods produced and/or consumed. The national mercury emission in China increased from 448 to 2151 tons during the 1980-2012 period. Nearly all of the emissions were ended up as exhaust gases and solid wastes. The proportion of exhaust gases decreased with increasing share of solid wastes and effluents. Of all the anthropogenic sources, coal was the most important contributor in quantity, followed by mercury mining, gold smelting, nonferrous smelting, iron steel production, domestic wastes, and cement production, with accounting for more than 90% of the total emission. There was a big variation of regional cumulative mercury emission during 1980-2012 in China, with higher emissions occurred in eastern areas and lower values in the western and far northern regions. The biggest cumulative emission occurred in GZ (Guizhou), reaching 3974 t, while the smallest cumulative emission was lower than 10 t in XZ (Tibet). Correspondingly, mercury accumulation in soil were higher in regions with larger emissions in unit area. Therefore, it is urgent to reduce anthropogenic mercury emission and subsequent impact on ecological functions and human health.

Enhanced Cd extraction of oilseed rape (Brassica napus) by plant growth-promoting bacteria isolated from Cd hyperaccumulator Sedum alfredii Hance.

Four plant growth-promoting bacteria (PGPB) were used as study materials, among them two heavy metal-tolerant rhizosphere strains SrN1 (Arthrobacter sp.) and SrN9 (Bacillus altitudinis) were isolated from rhizosphere soil, while two endophytic strains SaN1 (Bacillus megaterium) and SaMR12 (Sphingomonas) were identified from roots of the cadmium (Cd)/zinc (Zn) hyperaccumulator Sedum alfredii Hance. A pot experiment was carried out to investigate the effects of these PGPB on plant growth and Cd accumulation of oilseed rape (Brassica napus) plants grown on aged Cd-spiked soil. The results showed that the four PGPB significantly boosted oilseed rape shoot biomass production, improved soil and plant analyzer development (SPAD) value, enhanced Cd uptake of plant and Cd translocation to the leaves. By fluorescent in situ hybridization (FISH) and green fluorescent protein (GFP), we demonstrated the studied S. alfredii endophytic bacterium SaMR12 were able to colonize successfully in the B. napus roots. However, all four PGPB could increase seed Cd accumulation. Due to its potential to enhance Cd uptake by the plant and to restrict Cd accumulation in the seeds, SaMR12 was selected as the most promising microbial partner of B. napus when setting up a plant-microbe fortified remediation system.

An integrated approach to assess heavy metal source apportionment in peri-urban agricultural soils.

Three techniques (Isotope Ratio Analysis, GIS mapping, and Multivariate Statistical Analysis) were integrated to assess heavy metal pollution and source apportionment in peri-urban agricultural soils. The soils in the study area were moderately polluted with cadmium (Cd) and mercury (Hg), lightly polluted with lead (Pb), and chromium (Cr). GIS Mapping suggested Cd pollution originates from point sources, whereas Hg, Pb, Cr could be traced back to both point and non-point sources. Principal component analysis (PCA) indicated aluminum (Al), manganese (Mn), nickel (Ni) were mainly inherited from natural sources, while Hg, Pb, and Cd were associated with two different kinds of anthropogenic sources. Cluster analysis (CA) further identified fertilizers, waste water, industrial solid wastes, road dust, and atmospheric deposition as potential sources. Based on isotope ratio analysis (IRA) organic fertilizers and road dusts accounted for 74-100% and 0-24% of the total Hg input, while road dusts and solid wastes contributed for 0-80% and 19-100% of the Pb input. This study provides a reliable approach for heavy metal source apportionment in this particular peri-urban area, with a clear potential for future application in other regions.

Predictions of spatially averaged cadmium contents in rice grains in the Fuyang Valley, P.R. China.

Soils in the Fuyang valley (Zhejiang province, southeast China) have been contaminated by heavy metals. Since rice (Oryza sativa L.) is the dominant crop in the valley and because of its tendency to accumulate Cd in its grains, assessment of the human health risk resulting from consumption of locally produced rice is needed. In this study, we used a regression model to predict the average Cd content in rice grains for paddy fields. The multiple linear model for log(Cd) content in rice grains with log(HNO(3)-Cd), pH, log(clay), and log(soil organic matter, SOM) as predictors performed much better (R(2)(adj) = 66.1%) than the model with log(CaCl(2)-Cd) as a single predictor (R(2)(adj) = 28.1%). This can be explained by the sensitivity of CaCl(2)-extracted Cd for changes in redox potential and as a result of the drying of the soil samples in the laboratory. Consequently, the multiple linear model was used to predict the average Cd contents in rice grains for paddy fields, and to estimate the probability that the FAO/WHO standard of 0.2 mg kg(-1) will be exceeded. Eleven blocks had a probability smaller than 10% of exceeding this standard (safe blocks). If a lognormal distribution is assumed, 35 blocks had a probability larger than 90% (blocks at risk). Hence, risk reduction measures should be undertaken for the blocks at risk. For 27 blocks the probability was between 10 and 90%. For these blocks the uncertainty should be reduced via improvement of the regression model and/or increasing the number of sample locations within blocks.

Influence of EDDS on metal speciation in soil extracts: measurement and mechanistic multicomponent modeling.

The use of the [S,S]-isomer of EDDS to enhance phytoextraction has been proposed for the remediation of heavy metal contaminated soils. Speciation of metals in soil solution in the presence of EDDS and dissolved organic matter (DOM) received, however, almost no attention, whereas metal speciation plays an important role in relation to uptake of metals by plants. We investigated the influence of EDDS on speciation of dissolved metals in batch extraction experiments using fourfield-contaminated soils with pH varying between 4.7 and 7.2. Free metal concentrations were determined with the Donnan membrane technique, and compared with results obtained with the chemical speciation program ECOSAT and the NICA-Donnan model using a multicomponent approach. Addition of EDDS increased total metal concentrations in our soil extracts by a factor between 1.1 and 32 (Al), 2.1-48 (Cu), 1.1-109 (Fe), 1.1-5.5 (Ni), and 1.3-17 (Zn). In general, Al, Cu, Fe, and Zn had the largest total concentrations in the EDDS-treated extracts, but the contribution of these metals to the sum of total metal concentrations varied significantly between our soils. Free metal concentrations varied between 7.0 and 8.9 (pCd2+), 3.9-9.9 (pCu2+), 6.3-10.2 (pNi2+), and 5.2-7.0 (pZn2+). Addition of EDDS decreased free metal concentrations by a factor between 1.4 and 1.9 (Cd), 3.4-216 (Cu), 1.3-186 (Ni), and 1.3-3.3 (Zn). Model predictions of free metal concentrations were very good, and predicted values were mostly within 1 order of magnitude difference from the measured concentrations. A multicomponent approach had to be used in our model calculations, because competition between Fe and other metals for binding with EDDS was important. This was done by including the solubility of metal oxides in our model calculations. Multicomponent models can be used in chelant-assisted phytoextraction experiments to predict the speciation of dissolved metals and to increase the understanding of metal uptake by plants.

Mobilization of heavy metals from contaminated paddy soil by EDDS, EDTA, and elemental sulfur.

For enhanced phytoextraction, mobilization of heavy metals (HMs) from the soil solid phase to soil pore water is an important process. A pot incubation experiment mimicking field conditions was conducted to investigate the performance of three soil additives in mobilizing HMs from contaminated paddy soil (Gleyi-Stagnic Anthrosol): the [S, S]-isomer of ethylenediamine disuccinate (EDDS) with application rates of 2.3, 4.3, and 11.8 mmol kg(-1) of soil, ethylenediamine tetraacetate (EDTA; 1.4, 3.8, and 7.5 mmol kg(-1)), and elemental sulfur (100, 200, and 400 mmol kg(-1)). Temporal changes in soil pore water HM and dissolved organic carbon concentrations and pH were monitored for a period of 119 days. EDDS was the most effective additive in mobilizing soil Cu. However, EDDS was only effective during the first 24 to 52 days, and was readily biodegraded with a half-life of 4.1 to 8.7 days. The effectiveness of EDDS decreased at the highest application rate, most probably as a result of depletion of the readily desorbable Cu pool in soil. EDTA increased the concentrations of Cu, Pb, Zn, and Cd in the soil pore water, and remained effective during the whole incubation period due to its persistence. The highest rate of sulfur application led to a decrease in pH to around 4. This increased the pore water HM concentrations, especially those of Zn and Cd. Concentrations of HMs in the soil pore water can be regulated to a large extent by choosing the proper application rate of EDDS, EDTA, or sulfur. Hence, a preliminary work such as our pot experiment in combination with further plant experiments (not included in this study) will provide a good tool to evaluate the applicability of different soil additives for enhanced phytoextraction of a specific soil.

Organic micropollutants on river sediments from Rio de Janeiro State, Southeast Brazil

Este artigo pretende contribuir para o conhecimento sobre a concentração e destino de diferentes tipos de micro-poluentes num sistema fluvial tropical de uma região brasileira altamente industrializada. Os dados apresentados foram obtidos ao longo de três anos, como parte de um projeto de pesquisa internacional envolvendo instituições brasileiras e holandesas. As amostras de sedimentos foram obtidas da bacia hidrográfica Paraíba do Sul/Guandu, a mais importante hidrovia no Estado do Rio de Janeiro, onde 90 por cento da população depende dessa água para uso doméstico. Após extração com solventes não-polares num dispositivo sohxlet quente, e limpeza utilizando colunas cromatográficas, foram analisadas três classes de micro-poluentes orgânicos: inseticidas organoclorados (OCs), bifenis policlorados (PCBs) e outros hidrocarbonetos polinucleares (PAHs). Os organoclorados, inclusive os PCBs, estavam presentes em quantidades muito reduzidas nas amostras, provavelmente refletindo as restrições contra o uso dessa classe de compostos no mercado brasileiro. Entretanto, os PAHs mostravam níveis elevados ao redor de uma grande indústria siderúrgica na cidade de Volta Redonda. Tal contaminação deve-se, provavelmente, ao uso maciço de carvão nesta fábrica.

Organic micropollutants on river sediments from Rio de Janeiro State, Southeast Brazil.

The paper is a contribution for the knowledge upon concentrations and fate of different kinds of organic micropollutants in Tropical River system from a very industrialized region in Brazil. The presented data was obtained during three years of an International Research Project between Brazilian and Dutch institutions. The sediments were sampled at the Paraiba do Sul-Guandu river watershed, the most important watercourse of Rio de Janeiro state, where up 90% of the population depends on its water for domestic uses. After extraction with non-polar solvents in a hot sohxlet device and clean up using chromatographic columns, three classes of organic micropollutants were analyzed: organochlorine insecticides (OCs), polychlorinated biphenyls (PCBs) and polynuclear aromatic hydrocarbons (PAHs). The organochlorines, including the PCBs were scarcely present in the collected samples probably reflecting the restrictions of use of this class of compounds in the Brazilian market. However, the PAHs levels were high at the vicinity of a huge steelworks located in the city of Volta Redonda. This contamination is probably due to the massive use of coal in the above-cited metallurgical plant.

Dichlorodiphenyltrichloroethane in soil, river sediment, and fish in the Amazon in Brazil.

Dichlorodiphenyltrichloroethane (DDT), its main metabolites, and other organochlorines were analyzed in soils (n=6), fluvial sediments (n=14), and fish (n=10) that were collected in several areas of the Amazon region in Brazil. The samples were analyzed by capillary column gas chromatography coupled to electron capture detection. DDT residues were present in most of the collected sediments in concentrations of approximately 10 to 100 micro/kg (ppb, dry weight). Some urban top soils were found to have more than 1 mg/kg (ppm). In fish, as much as 0.5 mg/kg of total DDT (wet weight) was found in the edible parts. The presence of p,p'-DDT in most of the samples reflects the use of this insecticide against vectors of malaria between 1946 and 1993, which has led to its ubiquitous presence in the environment of the Brazilian Amazon.

Potentials and drawbacks of chelate-enhanced phytoremediation of soils.

Chelate-enhanced phytoremediation has been proposed as an effective tool for the extraction of heavy metals from soils by plants. However, side-effects related to the addition of chelates, e.g. metal leaching and effects on soil micro-organisms, were usually neglected. Therefore, greenhouse and lysimeter studies were conducted to study the phytoremedation potential of EDGA and citric acid and to evaluate its effects on microbial activity and leaching of Cd, Zn Cu and Pb. Grass, lupine and yellow mustard were grown on a moderately polluted acid (pH 4.5) sandy soil that contained 2 mg kg(-1) Cd and 200 mg kg(-1) Zn. Citric acid appeared to be degraded microbially within a few days after addition which limited its potential for long-lasting remediation studies. EDGA enhanced metal solubility but plant uptake did not increase accordingly. The metal shoot:root ratio increased upon addition of EDGA but it also reduced the net shoot and root biomass production of both lupine and yellow mustard. Bacterial biomass was higher in both the citric and EDGA treated pots but bacterial activity remained unaffected. The number of microbivorous nematodes was greatly reduced upon addition of EDGA which was most likely related to the reduced biomass production and, to a smaller extent, to the changes in the composition of the available food. Furthermore, EDGA enhanced metal leaching in the lysimeter study which could lead to groundwater pollution. To prevent these unwanted side-effects, careful management of phytoremediation methods, therefore, seems necessary.