土壤中苯并[a]芘和二苯并[a，h]蒽的快速测定及其降解特性研究

建立了加速溶剂萃取-高效液相色谱-二极管阵列检测(ASE-HPLC-PAD)快速测定土壤中苯并[a]芘(BaP)和二苯并[a.h]葸(DBA)的方法.通过提取剂、提取方法的优化,检测波长(BaP、DBA的λmax分别为294.6、295.8 nm)的选择,减少了干扰物的影响,提高了检测灵敏度.土壤中添加BaP、DBA的质量浓度均为0.02～0.50 mg/kg时,其平均回收率均为77.26%～109.56%,相对标准偏差为0.60%～2.74%;土壤中BaP、DBA的最小检测质量浓度分别为2.15、1.10μg/kg.将ASE-HPLC-PAD方法应用于污染场地土壤中BaP与DBA的测定及其降解特性研究表明,BaP与DBA的降解半衰期分别达210、693 d.     

不同化肥品种对水稻铬吸收和分配的影响

采用盆栽试验,研究在300mg/kg铬污染水稻土中分别施加氮肥(NH4Cl、NH4NO3、Ca(NO3)2和CO(NH2)2)、钾肥(K2SO4和KCl)、磷肥(Ca(H2PO4)2和NaH2PO4)对水稻生长以及吸收和分配铬的影响。结果表明:(1)施肥处理虽然增加了水稻的产量,但也改变了水稻植株对土壤铬的吸收和积累。从总体上看,不同施肥处理对水稻植株总铬的影响达到显著水平(p0.05);氮肥、钾肥处理的水稻植株总铬比对照处理增加了1.7%~72.9%,磷肥处理的水稻植株总铬比对照处理降低了2.1%~21.9%。(2)不同施肥处理明显影响了铬在水稻植株内的分配与迁移。受试的氮肥、钾肥不仅促进水稻根部对铬的吸收和累积,也促进了铬向地上部分迁移;而磷肥则降低了水稻根部对铬的吸收和累积以及铬向地上部分迁移。(3)受试8种不同施肥处理均显著提高了水稻糙米总铬,施肥处理后水稻成熟期糙米总铬为1.10~1.32mg/kg,均超过《食品中污染物限量》(GB 2762—2005)中铬的限量(粮食1.0mg/kg),比对照处理提高了139.1%~187.0%,增加了铬通过食物链威胁人体健康的风险。     

陕北黄土区土壤石油污染物对玉米生长影响研究

为研究陕北黄土区土壤石油污染物对玉米种子出苗率和幼苗生长的影响,采用盆栽试验的方法,设置土壤不同石油浓度处理组,培养玉米2个月,测定了各处理组玉米的出苗率、株高、茎宽、生物量和叶片叶绿素浓度.结果表明:(1)土壤石油质量浓度即使为30 g/kg时,各处理组出苗率最终均为100％;土壤石油质量浓度达到20 g/kg及以上时,在一定程度上会推迟玉米种子的出苗时间.(2)土壤石油质量浓度达到1 g/kg就会对玉米茎的生长产生抑制作用,可以显著降低玉米株高,但对玉米茎宽影响不显著.随着土壤石油浓度的升高,对玉米株高的抑制作用显著增加.玉米茎宽总体上是随着土壤石油浓度的升高而减小,但土壤石油质量浓度为0～1g/kg或20～30 g/kg时,玉米茎宽没有显著差异.(3)当土壤石油质量浓度达到5 g/kg以上时,植株干质量随石油浓度升高而减少.土壤石油质量浓度达到20 g/kg时,会显著降低玉米根的含水率;达到30 g/kg时,会显著降低茎和叶的含水率.(4)土壤石油质量浓度为1、5 g/kg时,叶绿素a和叶绿素b浓度与土壤石油质量浓度为0 g/kg时没有显著差异;土壤石油质量浓度为10、20、30 g/kg时,叶绿素a和叶绿素b浓度显著低于土壤石油质量浓度为0 g/kg时,并且随土壤石油浓度的升高呈降低趋势.     

不同钝化剂对降低水稻糙米Cd积累及土壤性状的影响

为探索降低重金属食物链污染风险的有效途径,在广东地区Cd污染稻田进行了4种钝化剂(腐殖酸钾、硅素调理剂、营养型阻控剂和复混钝化剂)田间小区试验,研究其对稻田土壤性状及水稻糙米Cd积累的影响。结果表明,与不加钝化剂的对照相比,钝化剂处理的水稻糙米Cd降低了19.7%(质量分数,下同)~60.5%,稻壳Cd降低了12.4%~52.1%,营养型阻控剂和腐殖酸钾降低糙米及稻壳Cd的效果较好。4种钝化剂对土壤pH、有效态Cd均无显著影响。相关分析和综合评价结果表明,水稻糙米Cd与土壤有效Ca和有效Mg呈显著负相关;4种钝化剂中,营养型阻控剂对Cd污染稻田的综合修复效果最好。     

碳酸钙和粉煤灰对铅胁迫下小麦毒害的缓解效应

采用室内盆栽和网室盆栽的方法,研究了碳酸钙和粉煤灰对铅污染土壤的小麦幼苗生物效应、成熟期籽粒含铅量和蛋白质含量及生物产量的影响,探讨了碳酸钙和粉煤灰缓解铅毒害小麦的生理机制.结果表明,在轻度铅污染(铅为350 mg/kg)的小麦农田,1.0 g/kg碳酸钙或50 g/kg粉煤灰对小麦生长有明显的促进作用.能有效缓解铅对小麦的毒害;在重度铅污染(铅为600mg/kg)的小麦农田,1.0～2.0 g/kg碳酸钙或50～100 g/kg粉煤灰对小麦铅毒害缓解效果较好.     

油菜对铜胁迫的生理响应及铜在茎杆和籽粒中的富集特征

以秦优九号为材料,通过盆栽试验研究了0、50、100、200、400mg/kg铜处理对油菜生长、产量、矿质元素含量的影响及铜在茎杆和籽粒中的富集特征.结果表明,低质量浓度(50mg/kg)铜处理,在一定程度上刺激了油菜的生长,植株的生物量、产量和矿质元素含量等指标均略高于对照或与对照相当,但差异不显著.随着土壤中铜浓度...     

桂林市表层土壤总汞分布特征研究

为了研究桂林市表层土壤汞污染情况,采集了不同功能区(包括校园区、风景旅游区、交通运输区、居民区、商业区、农业用地区和其他区域)的表层(0~10cm)土壤样品36个,采用硫酸-硝酸混合液浸提、原子荧光方法测定土壤中的总汞。结果表明,桂林市表层土壤的总汞质量浓度在0.136~1.873mg/kg,平均值为0.557mg/kg,中值为0.440mg/kg。各功能区土壤中汞的平均值均超过《土壤环境质量标准》(GB 15618—1995)的一级标准(0.15 mg/kg),以风景旅游区最高,为0.900 mg/kg,其次为商业区,为0.595 mg/kg。进一步对桂林市表层土壤总汞浓度与环境参数的关系进行了研究,结果表明,各采样点土壤的总汞浓度与有机质显著相关,与土壤pH无相关关系。     

气相色谱法同时测定苯系物和汽油化合物

气相色谱法具有较高的灵敏度和良好的线性关系。按照EPA QA／QC的要求,将该方法运用于实际样品分析。结果表明。水中汽油检出限为0．04mg／L。水中苯系物检出限为0．003-0．005mg／L,土壤中汽油检出限为0．5mg／kg,土壤中苯系物检出限为0.005-0．008mg／kg。样品加标回收率为97．1％～106．8％。变异系数为2．1％～4．6％,结果令人满意。     

贡湖湾退渔还湖区的基底稳定性的时空特征

2012年11月至2014年5月期间季度性对无锡贡湖湾退渔还湖生态修复工程进行跟踪调查与检测,就贡湖湾湿地土壤环境退渔还湖修复工程前后的理化性质进行了分析比较,用以评估修复工程实施后退渔还湖区基底的改善效果.结果表明:退渔还湖区内基底化学性质,有机质、总氮、总磷比退渔还湖初期分别提高241.59％、98.61％和162.86％.其中,有效氮和有效磷的均值为102.31 mg/kg和15.10 mg/kg,满足土壤养分分级标准Ⅲ级标准.有关基底稳定性物理性质与退渔还湖初期相比,土壤容重减少17.84％,pH值稳定在5.8 ～6.5之间,土壤缓冲能力明显提高,修复区南部(人为种植植物)的土壤团聚体稳定性恢复状况最好,西部(自然恢复)次之,北部(基底状况差,无植物种植)恢复状况低于前述两区.总之,贡湖退渔还湖修复区在经过17个月后,其基底的整体质量趋于良好,土壤各项养分及团聚体稳定性指标逐步达到合理水平,土壤环境已具有良好的生态功能.     

工业搬迁区绿化带土壤铜污染及其在植物体内的迁移

老工业搬迁区主要道路两旁绿化带土壤由于历经老工业企业的变迁和环境的污染破坏,可在一定程度上对这一地区环境的历史变迁及重金属污染状况起到指示作用。采集沈阳铁西老工业搬迁区绿化带土壤及其绿化乔木和灌木植株样品,分析土壤中铜的总量及生物有效态含量,同时分别分析了绿化乔木(8种)和绿化灌木(6种)植株根、枝条和叶片的含铜量。结果表明,搬迁区绿化带土壤中含铜量为29.14~166.95mg/kg,显著高于沈阳市土壤铜元素的背景值;土壤有效态铜为0.23~1.72mg/kg,达到中等水平(0.3~1.0mg/kg)的占采样点总数的70.0%。数据还显示,绿化乔木和灌木对铜的蓄积能力依品种不同差异显著,同种植物不同部位(根、枝条和叶片)对铜的富集能力不同;总体上,绿化乔木植株体内含铜量的分布规律为根叶片枝条或叶片根枝条,绿化灌木植株体内含铜量的分布规律为根叶片枝条。对铜蓄积能力较强的绿化乔木为榆叶梅(Amygdalus triloba Lindl.)、垂柳(Salix babylonica Linn.)、旱柳(Salix matsudana Koidz.)和银杏(Ginkgo biloba),对铜蓄积能力较强的绿化灌木为大叶女贞(Ligustrum lucidum Ait.)、小叶女贞(Ligustrum quihoui Carr.)和紫叶小檗(Berberis thunbergii cv.Atropurpurea)。     

Residues of chlorantraniliprole in rice field ecosystem

The fate of chlorantraniliprole was studied in rice field ecosystem, and a simple and reliable analytical method was developed for determination of chlorantraniliprole in soil, rice straw, paddy water and brown rice. Chlorantraniliprole residues were extracted from samples with acetonitrile. The extract was cleaned up with QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method, and determined by high-performance liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). The average recoveries were 76.9-82.4% from soil, 83.6-89.3% from rice straw, 95.2-103.1% from paddy water and 84.9-87.7% from brown rice. The relative standard deviation was less than 15%. The limits of detection (LODs) of chlorantraniliprole calculated as a sample concentration (S/N ratio of 3) were 0.012 μg L(-1) for paddy water, 0.15 μg kg(-1) for soil, brown rice and rice straw. The results of the kinetics study of chlorantraniliprole residue showed that chlorantraniliprole degradation in soil, water and rice straw coincided with C=0.01939e(-0.0434t), C=0.01425e(-0.8111t), and C=1.171e(-0.198t), respectively; the half-lives were about 16.0 d, 0.85 d and 3.50 d, respectively. The degradation rate of chlorantraniliprole in water was the fastest, followed by rice straw. The final residues of chlorantraniliprole on brown rice were lower than maximum residue limit (MRL) of 0.02 mg kg(-1) after 14 d Pre-Harvest Interval (PHI). Therefore, a dosage of 150 mL a.i.hm(-2) was recommended, which could be considered as safe to human beings and animals.     

Residues of carbosulfan and its metabolites carbofuran and 3-hydroxy carbofuran in rice field ecosystem in China

The fate of carbosulfan (seed treatment dry powder) was studied in rice field ecosystem, and a simple and reliable analytical method was developed for determination of carbosulfan, carbofuran, and 3-hydroxyl carbofuran in brown rice, rice straw, paddy water, and soil. The target compounds were extracted using acetonitrile or dichloromethane, cleaned up on acidic alumina or florisil solid phase extraction (SPE) cartridge, and analyzed by gas chromatography. The average recoveries of carbosulfan, carbofuran and 3-hydroxy carbofuran in brown rice, rice straw, paddy water, and soil ranged from 72.71% to 105.07%, with relative standard deviations of 2.00–8.80%. The limits of quantitation (LOQs) of carbosulfan, carbofuran and 3-hydroxy carbofuran in the samples (brown rice, rice straw, paddy water and soil) were 0.011, 0.0091, 0.014, 0.010 mg kg^?1, 0.016, 0.019, 0.025, 0.013 mg kg^?1, and 0.031, 0.039, 0.035, 0.036 mg kg^?1, respectively. The trials results showed that the half-lives of carbosulfan, carbofuran and 3-hydroxy carbofuran in rice straw were 4.0, 2.6 days, 3.9, 6.0 days, and 5.8, 7.0 days in Zhejiang and Hunan, respectively. Carbosulfan, carbofuran and 3-hydroxy carbofuran were detected in soils. Carbosulfan and 3-hydroxy carbofuran were almost undetectable in paddy water. Carbofuran was detected in paddy water. The final residues of carbosulfan, carbofuran and 3-hydroxy carbofuran in brown rice were lower than 0.05 mg kg^?1, which were lower than 0.5 mg kg^?1 (MRL of carbosulfan) or 0.1 mg kg^?1 (MRL of carbofuran). Therefore, a dosage of 420 g active ingredient per 100 kg seed was recommended, which could be considered as safe to human beings and animals. These would contribute to provide the scientific basis of using this insecticide.     

Copper contamination in paddy soils irrigated with wastewater

Copper (Cu) contamination was investigated in paddy soils where Cu-rich wastewater (12 mg Cu/l) was used for irrigation. The results showed that Cu contamination increased the soil Cu content from 17.0 mg Cu/kg in the non-wastewater irrigated soils (NWIS) to 101.2 mg Cu/kg in the wastewater irrigated soils (WIS), and Cu accumulated mostly in the surface layer (0-10 cm) of the paddy soil. The average Cu contents in brown rice, rice hull and rice straw from NWIS were 1.4, 7.3 and 14.5 mg Cu/kg, while those from WIS were 15.5, 133.2, and 101.4 mg Cu/kg, respectively. Correlation analysis revealed that the relationship between the Cu content in the rice straw and the rice hull with the total Cu content of the soil could be described by an exponential function (R2 = 0.921 and 0.831, respectively; P <0.01). Rice plants grown in the WIS showed symptoms of black roots, less effective tiller, etc. Subsequently, the rice yield decreased by 18-25%, compared with that grown in NWIS.     

Residues and dynamics of probenazole in rice field ecosystem

The simple and efficient method for determination of probenazole in soil, rice plant, and paddy water was developed, and the fate of probenazole in rice field ecosystem was also studied. Probenazole residues were extracted from sample, cleaned up by liquid/liquid partition and chromatographic column and then determined by gas chromatography with flame photometric detection. As far as the accuracy and precision was concerned, the method met certain standard. The LODs of probenazole calculated as a sample concentration (S/N ratio of 3) was 0.02 mg kg-1. The minimum detectable limit was 5x10(-10) g. The degradation of probenazole in soil, rice straw, and water was determined. The results showed that probenazole degradation in soil and rice straw coincided with C=0.576e-0.147t, C=17.858e-0.414t, respectively; the half-lives were about 4.7 and 1.7 d, respectively. The degradation rate of probenazole in rice straw was faster than that of in soil. Probenazole residue at 0.02 mg kg-1 could only be detected in paddy water within the first day after application. The final probenazole residues in soil, brown rice, and water were undetectable at levels of recommended and doubled dosage with an interval of 63 d. Therefore, a dosage of 1800-3600 g a.i. hm-2 was recommended, which could be considered as safe to human beings and animals. These would contribute to provide the scientific basis of using this fungicide.     

Cadmium (Cd) distribution and contamination in Chinese paddy soils on national scale

Rice is a staple food by an increasing number of people in China. As more issues have arisen in China due to rice contaminated by cadmium (Cd), Cd contamination in arable soils has become a severe problem. In China, many studies have examined Cd contamination in arable soils on a national scale, but little studies have focused on the distribution of Cd in paddy fields. This study explored the spatial pattern of Cd in paddy soils in China, made a preliminary evaluation of the potential risk, and identified the most critically contaminated regions based on the domestic rough rice trade flow. The results showed that Cd concentrations in paddy soils in China ranged from 0.01 to 5.50 mg/kg, with a median value of 0.23 mg/kg. On average, the highest Cd concentrations were in Hunan (0.73 mg/kg), Guangxi (0.70 mg/kg), and Sichuan (0.46 mg/kg) provinces. Cd concentrations in paddy soils in central and western regions were higher than those in eastern regions, especially the southeastern coastal regions. Of the administrative regions, Cd standard exceedance rate was 33.2 %, and the heavy pollution rate was 8.6 %. Regarding to Cd of paddy soil, soil environmental quality was better in Northeast China Plain than in Yangtze River Basin and southeastern coastal region. Mining activities were the main anthropogenic pollution source of Cd in Chinese paddy soil. Based on rice trade, more of the Chinese population would be exposed to Cd through intake of rice produced in Hunan province. Certain regions that output rice, especially Hunan province, should be given priority in the management and control of Cd contamination in paddy soil.     

Residues and dynamics of pymetrozine in rice field ecosystem

The fate of pymetrozine was studied in rice field ecosystem, and a simple and reliable analytical method for determination of pymetrozine in soil, rice straw, paddy water and brown rice was developed. Pymetrozine residues were extracted from samples, cleaned up by solid phase extraction (SPE) and then determined by high-performance liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS-MS). The average recovery was 81.2-88.1% from soil, 83.4-88.6% from rice straw, 87.3-94.1% from paddy water and 82.9-85.3% from brown rice. The relative standard deviation (RSD) was less than 15%. The limits of detection (LODs) of pymetrozine calculated as a sample concentration were 0.0003 mg kg⁻¹ (mg L⁻¹) for soil and paddy water, 0.001 mg kg⁻¹ for brown rice and rice straw. The results of kinetics study of pymetrozine residue showed that pymetrozine degradation in water, soil, and rice straw coincided with C = 0.194e^−0.986t, C = 0.044e^−0.099t, and C = 0.988e^−0.780t, respectively; the half-lives were about 0.70 d, 7.0 d and 0.89 d, respectively. The degradation rate of pymetrozine in water was the fastest, followed by rice straw. The highest final pymetrozine residues in brown rice were 0.01 mg kg⁻¹, which was lower than the EU’s upper limit of 0.02 mg kg⁻¹ in rice. Therefore, a dosage of 300-600 g a.i.hm⁻² was recommended, which could be considered as safe to human beings and animals.     

Effect of o-phenylenediamine on Cu adsorption and desorption in red soil and its uptake by paddy rice (Oryza sativa)

A study was carried out of Cu adsorption and desorption processes in red soil as affected by o-phenylenediamine (o-PD) in the range 0-80 mg/l. The results indicated that the presence of o-PD enhanced Cu adsorption in red soil in weakly acid media, meanwhile, desorption percentage of Cu from soil, extracted by 1.0 M MgCl(2), also increased when Cu adsorption in soil occurred in the presence of o-PD. The response of paddy rice to Cu in red soil shows that Cu toxicity was mitigated in the presence of o-PD and that the Cu concentration in rice straw decreased with increasing concentration of o-PD from 0 to 4.0 mmol/kg in soil. The fractions of background Cu in soil did not change noticeably in the presence of o-PD, whereas the effect of o-PD on the fractions of added Cu was significant. It was found that the exchangeable and carbonate bound Cu fractions decreased and the fraction of Cu bound to Fe-Mn oxides and organic matter increased with increasing o-PD concentration in soil when Cu was added at the same rate. Copper concentration in rice straw was significantly correlated with exchangeable Cu (r=0.961) and carbonate bound Cu (r=0.959) in soil. This result implicates that the behavior of Cu in soil is likely to be affected by organic pollutants containing amino groups.     

Evaluation of bioaugmentation and biostimulation on arsenic remediation in soil through biovolatilization

Arsenic (As) removal through microbially driven biovolatilization can be explored as a potential method for As bioremediation. However, its effectiveness needs to be improved. Biostimulation with organic matter amendment and bioaugmentation with the inoculation of genetic engineered bacteria could be potential strategies for As removal and site remediation. Here, the experiments were conducted to evaluate the impacts of rice straw and biochar amendment, inoculation of genetic engineered Pseudomonas putida KT2440 (GE P. putida) with high As volatilization activity, on microbial mediated As volatilization and removal from three different arseniferous soils. In general, the addition of rice straw (5%) significantly enhanced As methylation and volatilization in comparison with corresponding non-amended soils. Biochar amendments and inoculation of the GE P. putida increased As methylation and volatilization, respectively, but less than that of rice straw addition. The effectiveness of As volatilizations are quite different in the various paddy soils. The combined amendments of rice straw and GE P. putida exhibited the highest As removal efficiency (483.2 μg/kg/year) in Dayu soil, with 1.2% volatilization of the total As annually. The highest water-soluble As concentration (0.73 mg/kg) in this soil could be responsible for highest As volatilization besides the rice straw and bacteria in this soil.     

Remediation of cadmium-contaminated paddy soils by washing with calcium chloride: verification of on-site washing

We developed a new, three-step soil-wash method to remediate Cd-contaminated paddy fields. The method comprises (1) chemically washing the field soil with a CaCl2 solution; (2) washing the treated soil with water to eliminate residual Cd and CaCl2; and (3) on-site treatment of wastewater using a portable wastewater treatment system. Cd concentrations in the treated water were below Japan's environmental quality standard (0.01 mg Cd L-1), and the removal of Cd from the exchangeable fraction was 55% and from the acid-soluble fraction 15%. While soil fertility properties were affected by the soil washing, adverse effects were not crucial and could be corrected. The washing had no affect on rice growth, and reduced the average Cd concentration in rice grains by about two-thirds compared to a control plot. These results confirmed the effectiveness of the soil-wash method in remediating Cd-contaminated paddy fields.     

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.