Long-term assessment of the environmental fate of heavy metals in agricultural soil after cessation of organic waste treatments

The current study examined the anthropogenic accumulation and natural decrease in metal concentrations in agricultural soils following organic waste application. Three common organic wastes, including municipal sewage sludge, alcohol fermentation processing sludge, and pig manure compost (PMC), were applied annually to an agricultural soil under field conditions over 7 years (1994–2000) at a rate of 12.5, 25, and 50 ton ha^?1 year^?1 and the soil accumulation of three metals of concern (Cu, Pb, and Zn) was monitored. Subsequently, organic waste amendments ceased and the experimental plots were managed using conventional fertilization for another 10 years (2001–2010) and the natural decrease in metal concentrations monitored. Although Cu and Zn concentrations in all experimental plots did not exceed the relevant guideline values (150 mg kg^?1 for Cu and 300 mg kg^?1 for Zn), significant increases in metal concentrations were observed from cumulative application of organic wastes over 7 years. For instance, PMC treatment resulted in an increase in Cu and Zn from 9.8 and 72 mg kg^?1 to 108.2 and 214.3 mg kg^?1, respectively. In addition, the natural decrease in Cu and Zn was not significant as soils amended with PMC showed only a 16 and 19 % decline in Cu and Zn concentrations, respectively, even 10 years after amendment ceased. This research suggested that more attention must be paid during production of organic waste-based amendments and at the application stage.     

Response of roselle (Hibiscus sabdariffa) to heavy metals contamination in soils with different organic fertilisations

The response of green roselle (Hibiscus sabdariffa) to Cu/Pb contamination and manure application in soil was investigated using pot experiments. Subsamples of a mineral soil were treated with increasing doses (0–500 mg kg^?1) of Cu/Pb only and/or amended (at 10% w/w) with poultry or swine manure. Roselle plants were grown, monitored for changes in growth rate and post-harvest aboveground dry biomass and tissue Cu/Pb concentrations were determined. The plants were typically greenish with linear growth profiles at all metal doses, indicating some level of tolerance. Dry biomass yields decreased as metal dose increased. Poultry manure enhanced roselle biomass yields better than swine manure. Tissue Cu/Pb concentrations increased linearly as metal doses increased in unamended soils; whereas nonlinear responses were observed in manure-amended soils. Soil-to-plant transfer factors, T _f (%) indicated that Cu (13≤T _f (% )≤60) was more phytoavailable to roselle than Pb (11≤T _f (% )≤20). Tissue metal concentrations were modelled from soil pH, organic matter, plant available and pseudototal metal; but the models appeared more reliable with plant available metal as a covariate than with pseudototal metal content. These observations may become useful whenever phytoextraction is the remedial option for soils moderately contaminated by toxic metals.     

Assessment of heavy metals in a soil contaminated by oil spill: a case study in Nigeria

Surface and subsurface soil samples contaminated with crude oils were collected from an impacted site at Bodo City in the Niger Delta, Nigeria, after a field reconnaissance survey. An uncontaminated soil sample collected 100 m from the impacted site, but within the same geographical area, was used as a control. Trace elements such as, As, Cu, Cr, Cd, Fe, Pb, Ba, Ni, V, Hg and cation-exchange capacity constituents of the contaminated and uncontaminated soils were determined by atomic absorption spectroscopy. Trace element concentrations were: Cu, 0.5–13.4 mg kg^{? 1}; Cr, 0.2–0.8 mg kg^{? 1}; Fe, 6.2–8.7 mg kg^{? 1}; Ba 80.0–108.0 mg kg^{? 1}; Ni, 0.6–4.8 mg kg^{? 1}; and V, 4.0–9.4 mg kg^{? 1}; cation-exchange capacity ranged from 43.6 to 57.2 mg kg^{? 1} in surface and subsurface soils. Results showed that eigenvalues for the two first principal components represent up to 49% of the total variance. A positive correlation of the first principal component with Cu, Cr and cation-exchange capacity shows pollution from oil spillage, while a positive correlation of the second principal component with Cr, Fe, V, and dissolved oxygen (DO) shows both oil pollution and allochthonous inputs.     

Phytoextraction of Cr(VI) from soil using Portulaca oleracea

Cr(VI) represents an environmental challenge in both soil and water as it is soluble and bioavailable over a wide range of pH. In previous investigations, Portulaca oleracea (a plant local to the United Arab Emirates (UAE)) demonstrated particular ability for the phytoextraction of Cr(VI) from calcareous soil of the UAE. In this publication, the results of the evaluation of P. oleracea phytoextraction of Cr(VI) from UAE soil at higher concentrations are reported. P. oleracea was exposed to nine different concentrations of Cr(VI) in soil from 0 to 400 mg kg^?1. The uptake of Cr(VI) increased as its concentration in soil increased between 50 and 400 mg kg^?1, with the most efficient removal in the range from 150 to 200 mg kg^?1. The total chromium concentrations exceeded 4600 mg kg^?1 in roots and 1400 mg kg^?1 in stems, confirming the role of P. oleracea as an effective Cr(VI) accumulator. More than 95% of the accumulated Cr(VI) was reduced to the less toxic Cr(III) within the plant.     

Assessment of heavy metals contamination in soils surrounding a gold mine: comparison of two digestion methods

This study investigated two digestion methods (USEPA 3051: microwave, HNO₃ or Hossner: hot plate, HF–H₂SO₄–HClO₄) for heavy metals analysis in contaminated soil surrounding Mahad AD'Dahab mine, Saudi Arabia. Moreover, contamination metal levels were estimated. The Hossner and USEPA 3051 methods showed, respectively, average total contents of 17.2 and 18.1 mg kg^?1 for Cd, 11.6 and 10.6 mg kg^?1 for Co, 45.7 and 34.7 mg kg^?1 for Cr, 1030 and 1100 mg kg^?1 for Cu, 33,300 and 27,400 mg kg^?1 for Fe, 963 and 872 mg kg^?1 for Mn, 33.2 and 22.8 mg kg^?1 for Ni, 791 and 782 mg kg^?1for Pb, and 6320 and 2870 mg kg^?1 for Zn. A lack of significant differences and a high correlation coefficient (>90%) for Cd, Pb and Cu between the two digestion methods suggest that the total-recoverable method (USEPA 3051) may be equivalent to the total-total digestion method (Hossner) for determining these metals in the studied soil. However, significantly higher concentrations of Cr, Fe, Ni and Zn were found by the Hossner method comapred with the USEPA 3051 method. The soil samples have very or extremely high levels of Zn, Cu, Cd and Pb contamination, indicating very high potential ecological risk.     

Biosolids application affects the competitive sorption and lability of cadmium,copper, nickel,lead, and zinc in fluvial and calcareous soils

The objective of this research was to investigate the effects of biosolids on the competitive sorption and lability of the sorbed Cd, Cu, Ni, Pb, and Zn in fluvial and calcareous soils. Competitive sorption isotherms were developed, and the lability of these metals was estimated by DTPA extraction following their sorption. Sorption of all metals was higher in the fluvial than in the calcareous soil. Sorption of Cu and Pb was stronger than that of Cd, Ni, and Zn in all soils. Biosolids application (2.5%) reduced the sorption of all metals especially Cu and Pb (28–43%) in both soils (especially the calcareous soil) at the lower added metal concentrations (50 and 100 mg L^?1). However, it increased the sorption of all metals especially Pb and Cu in both soils (especially the calcareous soil; 15.5-fold for Cu) at the higher added concentrations (250 and 300 mg L^?1). Nickel showed the highest lability followed by Cd, Zn, and Pb in both soils. Biosolids increased the lability of the sorbed Ni in the fluvial soils at all added concentrations and the lability of Cd, Pb, and Zn at 50 mg L^?1, but decreased the lability of Cd, Pb, and Zn at 250 and 300 mg L^?1 in both soils. We conclude that at low loading rate (e.g., 50 mg L^?1) biosolids treatment might increase the lability and environmental risk of Cd, Cu, Pb, and Zn. However, at high loading rate (e.g., 300 mg L^?1) biosolids may be used as an immobilizing agent for Cd, Cu, Pb, Zn and mobilizing agent for Ni.     

Pomegranate husk as an adsorbent in the removal of toxic chromium from wastewater

The use of a new sorbent developed from the husk of pomegranate, a famous fruit in Egypt, for the removal of toxic chromium from aqueous solution has been investigated. The batch experiment was conducted to determine the adsorption capacity of the pomegranate husk. The effects of initial metal concentration (25 and 50 mg l^?1), pH, contact time, and sorbent concentration (2–6 g l^?1) have been studied at room temperature. A strong dependence of the adsorption capacity on pH was observed, the capacity increased as the pH decreased, and the optimum pH value was pH 1.0. Adsorption equilibrium and kinetics were studied with different sorbent and metal concentrations. The adsorption process was fast, and equilibrium was reached within 3 h. The maximum removal was 100% for 25 mg l^?1 of Cr⁶⁺ concentration on 5 g l^?1 pomegranate husk concentration, and the maximum adsorption capacity was 10.59 mg g^?1. The kinetic data were analysed using various kinetic models—pseudo-first-order, pseudo-second-order, Elovich, and intraparticle diffusion equations—and the equilibrium data were tested using several isotherm models, Langmuir, Freundlich, Tempkin, Dubinin–Radushkevich, and Generalized isotherm equations. The Elovich and pseudo-second-order equations provided the greatest accuracy for the kinetic data, while Langmuir and Generalized isotherm models were the closest fit for the equilibrium data. The activation energy of sorption has also been evaluated as 0.236 and 0.707 kJ mol^?1 for 25 and 50 mg l^?1 chromium concentration, respectively.     

Heavy metals and soil microbes

Heavy metal pollution is a global issue due to health risks associated with metal contamination. Although many metals are essential for life, they can be harmful to man, animal, plant and microorganisms at toxic levels. Occurrence of heavy metals in soil is mainly attributed to natural weathering of metal-rich parent material and anthropogenic activities such as industrial, mining, agricultural activities. Here we review the effect of soil microbes on the biosorption and bioavailability of heavy metals; the mechanisms of heavy metals sequestration by plant and microbes; and the effects of pollution on soil microbial diversity and activities. The major points are: anthropogenic activities constitute the major source of heavy metals in the environment. Soil chemistry is the major determinant of metal solubility, movement and availability in the soil. High levels of heavy metals in living tissues cause severe organ impairment, neurological disorders and eventual death. Elevated levels of heavy metals in soils decrease microbial population, diversity and activities. Nonetheless, certain soil microbes tolerate and use heavy metals in their systems; as such they are used for bioremediation of polluted soils. Soil microbes can be used for remediation of contaminated soils either directly or by making heavy metals bioavailable in the rhizosphere of plants. Such plants can accumulate 100 mg g^?1 Cd and As; 1000 mg g^?1 Co, Cu, Cr, Ni and 10,000 mg g^?1 Pb, Mn and Ni; and translocate metals to harvestable parts. Microbial activity changes soil physical properties such as soil structure and biochemical properties such as pH, soil redox state, soil enzymes that influence the solubility and bioavailability of heavy metals. The concept of ecological dose (ED₅₀) and lethal concentration (LC₅₀) was developed in response to the need to easily quantify the influence of pollutants on microbial-mediated ecological processes in various ecosystems.     

Effect of waterborne boron and molybdenum on survival,growth and feed intake of Indian major carp,Cirrhinus mrigala (Hamilton)

The effect of either boron (B) or molybdenum (Mo) on survival, growth and feed intake of Indian major carp, Cirrhinus mrigala (Hamilton), advanced fry was studied in two separate experiments. Survival rates of C. mrigala fry (2.78±0.14 g) following 50 days’ exposure to B at 0.01 (control), 0.5, 1.0, 2.0, 4.0 and 8.0 mg·L ^?1 were 100% at all concentrations except 8.0 mg·L ^?1 where the survival rate 87.5±7.5%. We observed 100% survival of mrigala fry at all concentrations of Mo, 0.02 (control), 0.5, 1.0, 2.0, 4.0 and 8.0 mg·L ^?1. Both B and Mo at 0.5 mg·L ^?1 showed significantly (p<0.05) higher growth of the fish compared with control and other concentrations. B exposure at 1.0, 2.0 and 4.0 mg·L ^?1 had no significant effect on growth rate, whereas at 8.0 mg B·L ^?1 growth of the fish almost ceased. Mo exposure at 1.0, 2.0, 4.0 and 8.0 mg·L ^?1 caused no significant effect on growth rate of the fish compared to control. Both B and Mo at all concentrations had no significant effect on feed intake of the fish compared with control, except at the highest concentration of boron (8.0 mg·L ^?1).     

四环素类抗生素和铜复合污染对猪粪厌氧消化的影响

兽用抗生素和矿物元素添加剂可起到预防动物疾病、促进动物生长、提高饲料转化率等作用,因此被广泛应用于畜禽养殖业。本研究以猪粪中温厌氧消化为研究目标,采用全自动甲烷潜势测试系统,考察了一定浓度的四环素(TC:30 mg·kg~(-1)dry weight,DW)、土霉素(OTC:50 mg·kg~(-1)DW)和金霉素(CTC:15 mg·kg~(-1)DW)对厌氧累积产甲烷量和日产甲烷速率的影响。结果表明,TC、OTC和CTC对猪粪中温厌氧消化累积产甲烷量和日产甲烷速率均有促进作用(累积产甲烷总量提高比例分别为7.9%、0.4%和5.4%)。另外,采用超高效液相色谱-四极杆串联质谱对猪粪厌氧消化前后样品中四环素类抗生素及其代谢产物进行了分析。结果表明,液相中的四环素类抗生素在猪粪厌氧消化过程中得到了明显的去除,去除率达到90%~100%;而固相中只有金霉素和差向异构金霉素有明显的去除效果,去除率分别为41.69%和41.58%。采用Tessier连续提取法对猪粪厌氧消化前后样品中5种形态的铜包括可交换态、碳酸盐结合态、铁锰氧化结合态、有机物结合态、残渣态进行了分析,结果表明,猪粪厌氧消化后,可交换态、碳酸盐结合态和铁锰结合态的铜浓度比厌氧消化前分别降低了1%~9%、0.1%~3%、12%~19%,而有机态和残渣态的铜浓度却在厌氧消化后分别增加了15%~35%、1%~2%。厌氧消化后,70%~80%的铜都是以有机铜的形态存在。铜逐渐从不稳定态转化为相对稳定的有机态和残渣态铜,因此,厌氧消化过程使铜从可生物利用态转变为不可生物利用态,趋于稳定化。     

Purification of contaminated paddy fields by clean water irrigation over two decades

Paddy fields near a mining site in north part of Guangdong Province, PR China, were severely contaminated by heavy metals as a result of wastewater irrigation from the tailing pond. The following clean water irrigation for 2 decades produced marked rinsing effect, especially on Pb and Zn. Paddy fields continuously irrigated with wastewater ever since mining started (50 years) had 1,050.0 mg kg^?1 of Pb and 810.3 mg kg^?1 of Zn for upper 20 cm soil, in comparison with 215.9 mg kg^?1 of Pb and 525.4 mg kg^?1 of Zn, respectively, with clean water irrigation for 20 years. Rinsing effect mainly occurred to a depth of upper 40 cm, of which the soil contained highest metals. Copper and Cd in the farmlands were also reduced due to clean water irrigation. Higher availability of Pb might partly account for more Pb transferred from the tailing pond to the farmland and also more Pb removal from the farmland as a result of clean water irrigation. Neither rice in the paddy field nor dense weeds in the uncultivated field largely took up the metals. However, they might contribute to activate metals differently, leading to a different purification extent. Rotation of rice and weed reduced metal retention in the farmland soil, in comparison with sole rice growth. Harvesting of rice grain (and partially rice stalk) only contributed small fraction of total amount of removed metal. In summary, heavy metal in paddy field resulted from irrigation of mining wastewater could be largely removed by clean water irrigation for sufficient time.     

Dynamic changes in radial oxygen loss and iron plaque formation and their effects on Cd and As accumulation in rice (Oryza sativa L.)

Temporal variations and correlations between radial oxygen loss (ROL), iron (Fe) plaque formation, cadmium (Cd) and arsenic (As) accumulation were investigated in two rice cultivars at four different growth stages based upon soil pot and deoxygenated solution experiments. The results showed that there were significant differences in ROL (1.1–16 μmol O₂ plant^?1 h^?1), Fe plaque formation (4,097–36,056 mg kg^?1), Cd and As in root tissues (Cd 77–162 mg kg^?1; As 49–199 mg kg^?1) and Fe plaque (Cd 0.4–24 mg kg^?1; As 185–1,396 mg kg^?1) between these growth stages. ROL and Fe plaque increased dramatically from tillering to ear emergence stages and then were much reduced at the grain-filling stage. Furthermore, significantly positive correlations were detected between ROL and concentrations of Fe, Cd and As in Fe plaque. Our study indicates that increased Fe plaque forms on rice roots at the ear emergence stage due to the increased ROL. This stage could therefore be an important period to limit the transfer and distribution of Cd and As in rice plants when growing in soils contaminated with these toxic elements.     

Denitrification in bottom sediment near oil production facilities off the Louisiana Gulf Coast

There is little information on denitrification in Gulf of Mexico bottom sediment. Potential denitrification rates in surface sediment were measured along transects legs extending 0–800 m from two offshore oil production platforms. The average potential denitrification ranged from approximately 50 mg N m^?2 d^?1 in surface sediment near the platforms to 15 mg N m^?2 d^?1 in sediment 800 m from the platforms. Measured denitrification rates were correlated to a higher organic matter content in sediment nearer the platforms. This research examined only a small component of nitrogen processing in Gulf of Mexico sediment. Additional research should examine the effect of nitrogen loading and temporal and spatial variability on denitrification rate.     

土壤中铜的生物可给性及其对人体的健康风险评价

为了研究土壤中铜的生物可给性与土壤理化性质之间的相互关系以及人体无意摄入土壤铜的风险,采集我国一些地区的15个土壤样品,利用in vitro方法研究了这些土壤中铜的生物可给性及其对人体的健康风险。结果表明,有2个土壤样品中铜的含量高过我国土壤环境质量标准的三级标准,有8个土壤样品中铜的含量高过二级标准;土壤中铜的溶解态浓度及其生物可给性变化很大,胃肠阶段铜的溶解态含量分别为5.2~308.8 mg·kg~(-1)和5.9~348.5 mg·kg~(-1),平均值分别为74.8 mg·kg~(-1)和82.0 mg·kg~(-1);而铜的生物可给性分别为183%~66.6%和213%~77.4%,平均值分别为442%和51.1%。胃阶段铜的生物可给性与土壤有机质和pH呈显著正相关,而与粘粒呈显著负相关,与铁铝氧化物有显著相关性;小肠阶段铜的生物可给性与土壤有机质和pH呈显著正相关,与土壤中总铜和锰氧化物含量呈显著负相关。如以胃阶段为判断,无意摄人土壤中铜对儿童的TDI(tolerable daily intake)贡献率除浙江富阳为2.51%外,有12个土壤样品低于1.00%,最低为0.11%。如以小肠阶段为判断,无意摄入土壤中铜对儿童的TDI贡献率除浙江富阳和浙江台州的土壤分别为2.83%和2.01%,另有12个土壤样品低于1.00%。可见,对于本研究中大多数土壤,通过口部无意摄入土壤中铜的对人体并没有很高的风险。     

Sulphamethazine in poultry manure changes carbon and nitrogen mineralisation in soils

Antibiotics are newly emerging organic pollutants in manure, soil, vegetables and water. Animal manure application might be leading to the accumulation of antibiotics in the farmland. However, the effect of sulphamethazine (SMZ) on the soil microbial community was scarcely investigated. This study was aimed to evaluate the impact of SMZ on poultry manure, on the structure and function of microbial community, carbon mineralisation, and changes in nitrogen forms in soil via an incubation experiment lasting 56?d. The treatments consisted of poultry manure at 1% wt (PM), PM containing 20?mg?kg^?1 SMZ (PM?+?20SMZ) and PM containing 100?mg?kg^?1 SMZ (PM?+?100SMZ), along with the untreated soil (control). Solid phase extraction was performed to measure the SMZ concentration in soils using high-pressure liquid chromatography. The cumulative CO₂-C was increased in all treated soils over the incubation period compared to the control. The PM?+?100SMZ had the highest increase in cumulative CO₂-C from the soil at 56?d of incubation. The treatment of PM?+?20SMZ showed a short-term decrease in nitrification rate in the soils at 1?d by altering the microbial community composition with 17% dissimilarity and decreasing the abundance of bacteria compared to PM-treated soil. The PM?+?100SMZ increased C mineralisation in the soil.     

Combination system of full-scale constructed wetlands and wetland paddy fields to remove nitrogen and phosphorus from rural unregulated non-point sources

Constructed wetlands (CWs) have been used effectively to remove nitrogen (N) and phosphorus (P) from non-point sources. Effluents of some CWs were, however, still with high N and P concentrations and remained to be pollution sources. Widely distributed paddy fields can be exploited to alleviate this concern. We were the first to investigate a combination system of three-level CWs with wetland paddy fields in a full scale to remove N and P from rural unregulated non-point sources. The removal efficiencies (REs) of CWs reached 57.3 % (37.4–75.1 %) for N and 76.3 % (62.0–98.4 %) for P. The CWs retained about 1,278 kg N ha^?1 year^?1 and 121 kg P ha^?1 year^?1. There was a notable seasonal change in REs of N and P, and the REs were different in different processing components of CWs. The removal rates of wetland paddy fields adopt “zero-drainage” water management according to local rainfall forecast and physiological water demand of crop growth reached 93.2 kg N ha^?1 year^?1 and 5.4 kg P ha^?1 year^?1. The rice season had higher potential in removing N and P than that in the wheat season. The whole combined system (0.56 ha CWs and 5.5 ha wetland paddy fields) removed 1,790 kg N year^?1 and 151 kg P year^?1, which were higher than those from CWs functioned alone. However, another 4.7-ha paddy fields were needed to fully remove the N and P in the effluents of CWs. The combination of CWs and paddy fields proved to be a more efficient nutrient removal system.     

The influence of solid matrices on arsenic toxicity to Corophium orientale

In marine ecosystems, benthic organisms are really important because they are the first step in the transfer of contaminants from environment to biota. To this end, this study focused on biological assays with the amphipod Corophium orientale exposed to two different molecules of arsenic: arsenate (As^V), the most abundant form in sediments, and dimethyl-arsinate (DMA), expected to be moderately toxic as an intermediate in the process of detoxification. The toxicity of arsenic compounds was measured after exposure to three different matrices: water, spiked natural sediment and inert spiked quartz sand. LC₅₀ values were calculated for each exposure, and the results confirmed the highest toxicity of As^V, in addition to underlining the importance of matrix of exposure. Water exposure was the matrix which presented the highest toxicity for inorganic arsenic (As^V LC₅₀=3.51 mg L^?1 vs DMA LC₅₀=54.65 mg L^?1), spiked natural sediment demonstrated its capability to chelate arsenate toxicity (As^V LC₅₀=34.27 mg kg^?1 vs. DMA LC₅₀=52.19 mg kg^?1) and spiked quartz sand presented intermediate values for As^V (LC₅₀=25.26 mg kg^?1), whereas for DMA a lower toxicity was registered (LC₅₀=872.35 mg kg^?1). This study can provide some useful data linked with chemical speciation of arsenic and exposure matrix, for improving the correct management of contaminated sediment.     

Hazardous metals in animal manure and their changes from 1990 to 2010 in China

Contents and changes of some hazardous elements in 388 animal feed and manure samples collected in 2009–2010 from 194 animal farms in 10 provinces of China were determined. The concentrations of Cu, Zn, Cr, and Pb in animal manures were in the ranges of 10–1800, 50–6300, 0.1–340, and 1.0–310 mg kg^?1, with median concentrations of 200, 500, 15, and 11 mg kg^?1, respectively. As, Cd, and Hg were in ranges from undetectable to 280, undetectable to 10, and 0.01–2.5 mg kg^?1, respectively. The concentrations of Cu, Zn, and As were highest in the manure from pig, followed by the manure from poultry and dairy cows. From 1990 to 2010, Cu, Zn, As, Cd, and Cr contents in manure increased strongly, especially in pig and poultry manure. Most of the increases occurred before 2003 and then stabilized or decreased which reflects the extensive use of feed additives before 2003 and the gradual stabilization since then.     

In vitro genotoxicity of extracellular extract from Nostoc piscinale

The extracellular extract obtained from 3 weeks incubation of the soil isolate cyanobacterium strain Nostoc piscinale GT-319 in BG-11 broth medium showed cytotoxic activity against Chinese Hamster Ovary (CHO) cells. Based on comet assay, a concentration of 333 µg mL^?1 (IC₅₀) produced DNA breakages in CHO cells. The concentration of 481 mg kg^?1 (LD₅₀) produced acute toxicity in mice at 48 h.