Phytoremediation of arsenic contaminated paddy soils with Pteris vittata markedly reduces arsenic uptake by rice

Arsenic (As) accumulation in food crops such as rice is of major concern. To investigate whether phytoremediation can reduce As uptake by rice, the As hyperaccumulator Pteris vittata was grown in five contaminated paddy soils in a pot experiment. Over a 9-month period P. vittata removed 3.5-11.4% of the total soil As, and decreased phosphate-extractable As and soil pore water As by 11-38% and 18-77%, respectively. Rice grown following P. vittata had significantly lower As concentrations in straw and grain, being 17-82% and 22-58% of those in the control, respectively. Phytoremediation also resulted in significant changes in As speciation in rice grain by greatly decreasing the concentration of dimethylarsinic acid (DMA). In two soils the concentration of inorganic As in rice grain was decreased by 50-58%. The results demonstrate an effective stripping of bioavailable As from contaminated paddy soils thus reducing As uptake by rice.     

Dynamics of PCB removal and detoxification in historically contaminated soils amended with activated carbon

Activated carbon (AC) can help overcome toxicity of pollutants to microbes and facilitate soil bioremediation. We used this approach to treat a Histosol and an Alluvial soil historically contaminated with PCB (4190 and 1585 mg kg⁻¹, respectively; primarily tri-, tetra- and pentachlorinated congeners). Results confirmed PCB persistence; reductions in PCB extractable from control and AC-amended soils were mostly due to a decrease in tri- and to some extent tetrachlorinated congeners as well as formation of a bound fraction. Mechanisms of PCB binding by soil and AC were different. In addition to microbial degradation of less chlorinated congeners, we postulate AC catalyzed dechlorination of higher chlorinated congeners. A large decrease in bioavailable PCB in AC-amended soils was demonstrated by greater clover germination and biomass. Phytotoxicity was low in treated soils but remained high in untreated soils for the duration of a 39-month experiment. These observations indicate the utility of AC for remediation of soils historically contaminated with PCB.     

Phytotoxicity of atrazine and alachlor in soil amended with sludge,manure and activated carbon

Abstract

Greenhouse studies were conducted to determine the influence of waste‐activated carbon (WAC), digested municipal sewage sludge (DMS), and animal manure on herbicidal activity of atrazine [2‐chloro‐4‐(ethylamino)‐6‐(isopropylamino)‐s‐trazine] and alachlor [2‐chloro‐2’,6'‐diethyl‐N‐(methoxymethyl)acetanilide] in a Plainfield sandy soil. Amendments generally reduced bioactivity against oat (Avena sativa L.) and Japanese millet (E. crus‐galli frumentacea). The extent to which herbicide phytotoxicity was inhibited depended upon the application rate and the kind of soil amendment. WAC, applied at the loading rate of 2.1 mt C/ha, showed a significant inhibitory effect on both herbicides. In DMS‐ and manure‐amended soil, the reduction of atrazine activity was not significant at the rate of 8.4 mt C/ha, but reduction of alachlor activity was significant at the rate of 4.2 mt C/ha. Despite inhibition of herbicidal activity, the ED₅₀ of atrazine and alachlor was below 2 ppm in most of the amendment treatments. Before adopting carbon‐rich waste amendments as management practices for controlling pesticide leaching in coarse‐textured soils, further studies are needed to characterize how alterations in sorption, leaching and degradation may affect herbicidal activity.     

Effects of root anatomy and Fe plaque on arsenic uptake by rice seedlings grown in solution culture

Hydroponic experiments were carried out to investigate the effects of root anatomy, induced by aeration and stagnation, and Fe plaque on arsenic (III&V) uptake and translocation by rice plants. The results showed that As uptake in rice plants (Gui Chao-2) treated by aeration was decreased due to lower root specific surface area. Rice roots with larger specific surface area tended to form more Fe plaque, and Fe plaque affected As uptake kinetics by changing As influx curves from linear to hyperbolic for As(III) and from hyperbolic to S-curve for As(V). Fe plaque increased As(III&V) adsorption and minimized the effects of root anatomy characteristics on As uptake into roots and subsequently translocation to shoots. Fe plaque increased As(III) uptake rate at As(III) concentrations of 0.5∼8 mg L⁻¹, reduced As(V) uptake rate at low As(V) concentrations (<2 mg L⁻¹), but increased As uptake rate at high As(V) concentrations (>6 mg L⁻¹).     

Effects of rapeseed residue on lead and cadmium availability and uptake by rice plants in heavy metal contaminated paddy soil

Rapeseed (Brassica napus L.) has been cultivated for biodiesel production worldwide. Winter rapeseed is commonly grown in the southern part of Korea under a rice-rapeseed double cropping system. In this study, a greenhouse pot experiment was conducted to assess the effects of rapeseed residue applied as a green manure alone or in combinations with mineral N fertilizer on Cd and Pb speciation in the contaminated paddy soil and their availability to rice plant (Oryza sativa L.). The changes in soil chemical and biological properties in response to the addition of rapeseed residue were also evaluated. Specifically, the following four treatments were evaluated: 100% mineral N fertilizer (N100) as a control, 70% mineral N fertilizer + rapeseed residue (N70 + R), 30% mineral N fertilizer + rapeseed residue (N30 + R) and rapeseed residue alone (R). The electrical conductivity and exchangeable cations of the rice paddy soil subjected to the R treatment or in combinations with mineral N fertilizer treatment, N70 + R and N30 + R, were higher than those in soils subjected to the N100 treatment. However, the soil pH value with the R treatment (pH 6.3) was lower than that with N100 treatment (pH 6.9). Use of rapeseed residue as a green manure led to an increase in soil organic matter (SOM) and enhanced the microbial populations in the soil. Sequential extraction also revealed that the addition of rapeseed residue decreased the easily accessible fraction of Cd by 5-14% and Pb by 30-39% through the transformation into less accessible fractions, thereby reducing metal availability to the rice plant. Overall, the incorporation of rapeseed residue into the metal contaminated rice paddy soils may sustain SOM, improve the soil chemical and biological properties, and decrease the heavy metal phytoavailability.     

柠檬酸对褐土中DTPA提取态铜、镉含量及对紫花苜蓿吸收铜、镉的影响

为了阐述有机酸对土壤中重金属生物有效性的影响,通过盆栽实验,研究了Cu、Cd复合污染下柠檬酸对褐土中二乙基三胺五乙酸(DTPA)提取态铜和镉含量的影响,并探讨了柠檬酸对植物吸收铜、镉的影响。结果表明,土壤中DT-PA-Cu含量随柠檬酸添加量的增加而减小,添加高浓度铜(Cu 1 000)处理中,DTPA-Cu含量减小更明显。在添加低铜浓度(Cu600)处理下,柠檬酸添加量为2和12 mmol/kg时,土壤DTPA-Cu含量随土壤镉含量的增加而增加,而柠檬酸含量为5mmol/kg时,DTPA-Cu含量在低镉处理(Cd 1)时含量最低。紫花苜蓿中铜含量随柠檬酸添加量的增加明显降低。土壤中DTPA-Cd含量随柠檬酸添加量的增加而减小,且随铜添加量的增加而降低。紫花苜蓿中的镉含量随柠檬酸添加量的增加先增加后减小;在相同柠檬酸添加量处理时,紫花苜蓿中镉的含量随镉含量的增加而增加;在低镉处理下,铜的加入对较低柠檬酸浓度时紫花苜蓿镉含量影响不明显,但柠檬酸浓度为12 mmol/kg时,紫花苜蓿中镉含量随铜添加量的增加而明显增加。     

FeCl3-柠檬酸对土壤中Pb和Cd淋洗动力学特征

采集辽宁省某锌厂周边农田耕作层（0~20 cm）土壤样品,以FeCl3-柠檬酸为淋洗剂,研究在不同pH、温度和离子强度的实验条件下,其对土壤中Pb和Cd的淋洗动力学特征及淋洗机理。结果表明,在实验条件下,随淋洗时间延长,土壤中Cd、Pb的淋洗量不断增加,Pb、Cd的淋洗过程可分为快速反应阶段、慢速反应阶段和解吸平衡阶段;当pH=3、4、5和6,温度为25、35和45℃,离子强度为0.01、0.05、0.2和0.5 mol·L-1时,描述土壤中Pb、Cd淋洗动力学过程时Elovich方程（R2=0.787 0~0.994 8,SE=0.000 2~0.024 2）均优于双常数方程（R2=0.819 2~0.995 5,SE=0.007 6~0.294 5）优于一级动力学方程（R2=0.219 8~0.632 1,SE=0.052 9~0.815 5）,说明在不同环境条件下,该淋洗动力学过程为非均相扩散过程;随pH（6~3,pH=5除外）降低、温度（25~45℃）升高和CaCl2浓度（0.01~0.5 mol·L-1）升高,Pb、Cd淋洗量均增大。     

不同比例乙酸和丙酸对活性污泥微生物合成聚羟基脂肪酸酯的影响

聚羟基脂肪酸酯（PHA）是一种生物可降解塑料,利用活性污泥合成PHA具有节约成本、操作方便的优点。研究选择污泥发酵液挥发性脂肪酸（VFAs）中比重相对较高的乙酸和丙酸作为碳源自配营养液,深入研究不同质量浓度比对PHA合成的影响。结果表明,乙酸为主要碳源时更有利于PHA的合成,最大合成量12.3%出现在乙酸作为唯一碳源的条件下。此外,PHA合成量随着底物中有机酸比重的增加而增加,充分展现了利用挥发性脂肪酸大量合成PHA的良好前景。     

腐植酸对多环芳烃在污染土壤中淋出及截留分解的效果研究

多环芳烃是固废拆解地一类污染较严重的有毒有机物质,用腐植酸作表面活性剂淋洗污染土壤起到较好的增溶及截留分解污染物的作用,达到修复污染土壤的目的。实验结果表明,随着腐植酸加入量的增加,菲、萘、荧蒽、芘和∑PAHs的淋出量显著提高,在污染红壤中最大淋出率分别为52.9%、70.1%、30.5%、46.1%和42.8%,在污染水稻土中最大淋出率分别为51.8%、67.3%、35.0%、38.3%和35.5%,同时多环芳烃的截留分解率也相对较高,而污染红壤和水稻土的总修复率分别达到56.3%和49.8%。     

The influence of pH and organic matter content in paddy soil on heavy metal availability and their uptake by rice plants

The experiments were done to investigate the effect of soil pH and organic matter content on EDTA-extractable heavy metal contents in soils and heavy metal concentrations in rice straw and grains. EDTA-extractable Cr contents in soils and concentrations in rice tissues were negatively correlated with soil pH, but positively correlated with organic matter content. The combination of soil pH and organic matter content would produce the more precise regression models for estimation of EDTA-Cu, Pb and Zn contents in soils, demonstrating the distinct effect of the two factors on the availability of these heavy metals in soils. Soil pH greatly affected heavy metal concentrations in rice plants. Furthermore, inclusion of other soil properties in the stepwise regression analysis improved the regression models for predicting straw Fe and grain Zn concentrations, indicating that other soil properties should be taken into consideration for precise predicting of heavy metal concentrations in rice plants.     

Effect of external iron and arsenic species on chelant-enhanced iron bioavailability and arsenic uptake in rice (Oryza sativa L.)

This study was conducted to investigate the effect of external iron status and arsenic species on chelant-enhanced iron bioavailability and arsenic uptake. Rice seedlings (Oryza sativa L.) were used as model plant, and were grown in artificially contaminated sandy soils irrigated with Murashige and Skoog (MS) culture solution. Arsenate uptake in roots and shoots of rice seedlings were affected significantly (p > 0.05) while dimethylarsinic acid (DMAA) was not by the additional iron and chelating ligand treatments. Regardless of iron concentrations in the soil solution, HIDS increased arsenic uptake for roots more than EDTA and EDDS. Chelating ligands and arsenic species also influenced iron uptake in rice roots. Irrespective of arsenic species, HIDS was found to be more effective in the increase of iron bioavailability and uptake in rice roots compared to other chelants. There was a significant positive correlation (r = 0.78, p < 0.05) between arsenate and iron concentrations in the roots of rice seedlings grown with or without additional iron indicating that arsenate inhibit iron uptake. In contrast, there was no correlation between iron and DMAA uptake in roots. Poor correlation between iron and arsenic in shoots indicated that iron uptake in shoots was neither affected by additional iron nor by arsenic species. Compared to the control, chelating ligands increased iron uptake in shoots of rice seedlings significantly (p < 0.05). Regardless of additional iron and arsenic species, iron uptake in rice shoots did not differed among EDTA, EDDS, and HIDS treatments.     

Uptake of selected PAHs from contaminated soils by rice seedlings (Oryza sativa) and influence of rhizosphere on PAH distribution

The uptake of selected polycyclic aromatic hydrocarbons (PAHs) by rice (Oryza sativa) seedlings from spiked aged soils was investigated. When applied to soils aged for 4 months, naphthalene, phenanthrene, and pyrene exhibited volatilization loss of 98, 95, and 30%, respectively, with the remaining fraction being fixed by soil organic matter and/or degraded by soil microbes. In general, concentrations of the three PAHs in rice roots were greater than those in the shoots. The concentrations of root associated PHN and PYR increased proportionally with both soil solution and rhizosphere concentrations. PAH concentrations in shoots were largely independent of those in soil solution, rice roots, or rhizosphere soil. The relative contributions of plant uptake and plant-promoted rhizosphere microbial biodegradation to the total mass balance were 0.24 and 14%, respectively, based on PYR concentrations in rhizosphere and non-rhizosphere soils, the biomass of rice roots, and the dry soil weight.     

Changes of organic acid exudation and rhizosphere pH in rice plants under chromium stress.

The effect of chromium (Cr) stress on the changes of rhizosphere pH, organic acid exudation, and Cr accumulation in plants was studied using two rice genotypes differing in grain Cr accumulation. The results showed that rhizosphere pH increased with increasing level of Cr in the culture solution and with an extended time of Cr exposure. Among the six organic acids examined in this experiment, oxalic and malic acid contents were relatively higher, and had a significant positive correlation with the rhizosphere pH, indicating that they play an important role in changing rhizosphere pH. The Cr content in roots was significantly higher than that in stems and leaves. Cr accumulation in plants was significantly and positively correlated with rhizosphere pH, and the exudation of oxalic, malic and citric acids, suggesting that an increase in rhizosphere pH, and exudation of oxalic, malic and citric acid enhances Cr accumulation in rice plants.     

Fe/AC內电解-H2O2联合技术降解浮选废水中苯胺黑药

研究了Fe/AC內电解-H2O2联合技术在降解浮选废水中浮选药剂苯胺黑药（DDA）的效果及可行性。通过正交和单因素实验,考察了其工艺条件参数对DDA和COD处理效果的影响。结果表明,在初始pH=3,Fe/AC质量比为2：1,H2O2投加量为0.6 mmol·L-1,Fe/AC IME和Fenton氧化工段HRT分别为60 min和20 min的条件下,模拟废水DDA和COD浓度由200 mg·L-1、395 mg·L-1分别降至28.7 mg·L-1和32.9 mg·L-1,去除率分别高达85.6%和91.7%。Fe/AC IME-H2O2连续处理实际浮选废水（COD 880~910 mg·L-1）96 h后,COD去除率仍维持在88.0%以上,残留浓度低于《污水综合排放标准》（GB 8978-1996）二级标准值。     

3种纳米材料对低分子质量有机酸淋洗铅、锌和镉效率的影响

新型高效淋洗剂的筛选是土壤重金属淋洗修复技术的基础之一。通过振荡淋洗法研究了纳米二氧化钛（TiO2）、碳纳米管（C）和纳米二氧化硅（SiO2）与柠檬酸和酒石酸组合改性后对2种铅锌矿区土壤的淋洗效率。结果表明,单一柠檬酸对土壤Pb、Zn和Cd去除率最高为71.28%、61.09%、57.40%,而单一纳米材料对3种重金属去除率均小于2%;2种有机酸与纳米材料改性后的重金属淋洗率与单独淋洗差异显著（P2浓度升高,2种有机酸对2种土壤中Pb的去除率显著降低（P2能够明显提升2种有机酸对土壤Pb、Zn和Cd的去除率（P2分别在0.04 mol·L-1和0.10 mol·L-1时提高柠檬酸对3种金属的去除率达13.1%~25.1%和13.5%~26.8%。     

Zero-valent iron and iron oxide-coated sand as a combination for removal of co-present chromate and arsenate from groundwater with humic acid

The combination of zero-valent iron (Fe⁰) and iron oxide-coated sand (IOCS) was used to remove Cr(VI) and As(V) from groundwater in this study. The efficiency and the removal mechanism of Cr(VI) and As(V) by using this combination, with the influence of humic acid (HA), were investigated using batch experiments. Results showed that, compared to using Fe⁰ or IOCS alone, the Fe⁰-IOCS can perform better on the removal of both Cr(VI) and As(V). Metal extraction studies showed that As(V) was mainly removed by IOCS and iron corrosion products while Cr(VI) was mainly removed by Fe⁰ and its corrosion products. Competition was found between Cr(VI) and As(V) for the adsorption sites on the iron corrosion products. HA had shown insignificant effects on Cr(VI) removal but some effects on As(V) removal kinetics. As(V) was adsorbed on IOCS at the earlier stage, but adsorbed/coprecipitated with the iron corrosion products at the later stage.     

Simultaneous extraction of Cr(VI) and Cu(II) from humic acid with new synthesized EDTA derivatives

Soil washing is one of the few permanent treatment alternatives for removing metal contaminants. Ethylenediaminetetraacetic acid and its salts (EDTA) is very effective at removing cationic metals and has been utilized globally. However it is ineffective for anionic metal contaminants or metals bound to soil organic matter. The simultaneous removal of cationic and anionic metal contaminants by soil washing is difficult due to differences in their properties. The present study evaluated the potential of a washing process using two synthesized EDTA-derivatives, C₆HEDTA (2,2′-((2-((carboxymethyl)(2-(hexanoyloxy)ethyl)amino)ethyl)azanediyl)diacetic acid) and C₁₂HEDTA (2,2′-((2-((carboxymethyl) (2-(dodecanoyloxy)ethyl)amino)ethyl)azanediyl)diacetic acid), which consist of a hydrophilic polycarboxylic moiety and a hydrophobic moiety with a monoalkyl ester group. A series of equilibrium batch experiments at room temperature were conducted to investigate the efficacy of C₆HEDTA and C₁₂HEDTA as extractants for both oxyanion Cr(VI) and cationic Cu(II). Results showed that either C₆HEDTA or C₁₂HEDTA can extract both Cr(VI) and Cu(II) from humic acid simultaneously. However, C₆HEDTA was less effective for Cr(VI) probably because it has no surface activities to increase solubility of humic acid, like C₁₂HEDTA. Extraction of Cr(VI) was mainly attributed to the decreased surface tension and enhanced solubility of organic matter. Extraction of Cu(II) was attributed to both the Cu(II) chelation and enhanced solubility of humic acid. It was demonstrated that the hydrophilic polycarboxylic moiety of C₁₂HEDTA chelates cations while the monoalkyl ester group produces surface active properties that enhance the solubility of humic acid.     

模拟酸雨对磷酸二氢钾钝化污染土壤Cu、Cd、Pb和P释放的影响

以磷酸二氢钾(PDP)钝化后的重金属污染土壤为研究对象,通过室内土柱淋溶实验,考察在pH为3.5、4.5和5.6的模拟酸雨作用下土壤Cu、Cd、Pb和P的释放特征。结果表明:PDP处理较对照处理显著增加了淋出液中pH、电导率(EC)和总有机碳(TOC)含量,但不同pH模拟酸雨对对照和PDP处理淋出液pH、EC和TOC含量影响较小。对照处理中,正磷酸盐含量维持在较低水平(0.02~0.13 mg·L-1);PDP处理下,正磷酸盐含量在1~3 L和4~12 L分别是《地表水环境质量标准》(GB 3838-2002)五类水标准(总磷含量0.4 mg·L-1)的55.1~819倍和9.46~46.6倍,对地表水表现出较大的富营养化风险。PDP处理较对照处理显著降低了淋溶初期淋出液中的Cu、Cd和Pb含量,但是随模拟酸雨pH降低,对照和PDP处理的土壤淋出液中Cu、Pb含量均未表现出显著差异。因此,PDP处理能够显著钝化污染土壤中的Cu、Cd和Pb,但需关注酸雨淋溶下过量磷释放对地表水富营养化的潜在风险。     

Vertical distribution and environmental significance of sulfur and oxygen heterocyclic aromatic hydrocarbons in soil samples collected from Beijing, China

Vertical distribution of the concentration and composition of some sulfur and oxygen heterocyclic aromatic hydrocarbons (SOHAHs), such as, fluorene, dibenzofuran, dibenzothiophene and their alkyl homologues in 10 soil profiles in Beijing have been investigated. The results showed that the concentrations and composition of SOHAHs in topsoil (0-30cm) from different profiles are different. The concentrations of SOHAHs in topsoils are much higher than that in bottom soils where the concentrations are relatively constant. The fingerprints of SOHAHs from same profile are similar in topsoil samples, which are obviously different at the deep part, which suggested that the sources of these compounds are consistent in topsoil and are discriminating between surface and bottom soils. The main sources of SOHAHs in surface soil were fossil fuel combustion, petroleum and wastewater irrigation, while those at deep part were likely derived from the degradation products of soil organic matters.     

Background levels of Persistent Organic Pollutants in humans from Taiwan: Perfluorooctane sulfonate and perfluorooctanoic acid

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) have recently received attention due to their widespread contamination of the environment. PFOS and PFOA are stable in the environment and resistant to metabolism, hydrolysis, photolysis and biodegradation. PFOS and PFOA have been found in human blood and tissue samples from both occupationally exposed workers and the general worldwide population. This study aimed to determine the background levels of PFOS and PFOA in the Taiwanese population, investigate related factors, and compare exposure in Taiwan to that in other countries. The concentration of PFOS in the 59 serum samples collected from the general population in Taiwan ranged from 3.45 to 25.65 ng mL⁻¹ (median: 8.52), and the concentration of PFOA ranged from 1.55 to 7.69 ng mL⁻¹ (median: 3.22). There was a significant positive correlation (r = 0.51; p < 0.0001) between PFOS and PFOA concentrations. Males had higher concentrations of PFOA and PFOS than females. PFOS levels in serum increased with age. This study is the first investigation to reveal the PFOS and PFOA levels of serum samples in the general population of Taiwan. The levels of PFOS and PFOA in Taiwanese serum samples were comparable with those from other countries (PFOS: 5.0–35 ng mL⁻¹, PFOA: 1.5–10 ng mL⁻¹).