Sorption and desorption of pymetrozine on six Chinese soils

Pymetrozine is a selective insecticide with a unique chemical structure and mode to control hemipteran and homopteran. While pymetrozine has brought great benefits to crop production by killing insects, its residues in soil may have a detrimental effect on environment. Therefore, it is of great importance to investigate its behaviors in soil. In this study, the sorption and desorption of pymetrozine on six Chinese soils were investigated using a batch equilibrium approach to understand its mobile behavior in the soils. Both sorption and desorption isotherms of pymetrozine were in good agreement with the Freundlich model. The sorption coefficient K_F varied between 3.37 and 58.32 mL∙g⁻¹ and the sorption isotherms were nonlinear, with 1/n ranging from 0.57 to 0.91. A regression equation was proposed to predict the sorption of pymetrozine on six different soil samples: log K_F = 4.3708 − 4.5709 × log (pH in 0.01mol·L⁻¹ CaCl₂) + 0.4700 × log OC% + 0.0057 × sand (%) + 0.0022 × CEC(clay), with R² = 0.9982. The organic carbon content of soil positively affected the sorption of pymetrozine, but soil pH had a negative effect on the sorption. Additionally, effects of CaCl₂ concentration, soil to solution ratio and pesticide form were investigated. The sorption was promoted with an increase in soil to solution ratio and a decrease in CaCl₂ concentration. The possible variation of the five formulated products of pymetrozine was also investigated.     

神木煤矿区土壤重金属污染特征研究

通过对神府煤田开采区3个煤矿区周围土壤Cu、Cd、Cr、Mn、Ni质量分数进行测定及分析,评价了煤田开采对周围土壤的污染程度。结果表明,长期的煤炭资源开发、运输等活动,已导致周围土壤受到重金属不同程度的累积性污染,土壤中Cd、Ni质量分数高于陕西省土壤背景值,且Cd污染程度较高,Ni污染程度较低,而Cu、Cr、Mn基本不受污染。3个煤矿表层土壤各重金属元素质量分数均表现出污染区大于对照区,但这种变化幅度存在一定差异;Cu、Cr、Mn 3种重金属元素虽没有超出背景值,但已表现出一定程度的累积;煤矿周围土壤重金属污染受到开采年限、土壤质地、风向等因素的影响。3个煤矿污染区土壤剖面样品中,5种重金属元素质量分数基本上随着土壤深度的增加呈现降低的趋势,且这种趋势具有波动性。     

神木煤矿区土壤重金属污染特征研究

通过对神府煤田开采区3个煤矿区周围土壤Cu、Cd、Cr、Mn、Ni质量分数进行测定及分析,评价了煤田开采对周围土壤的污染程度。结果表明,长期的煤炭资源开发、运输等活动,已导致周围土壤受到重金属不同程度的累积性污染,土壤中Cd、Ni质量分数高于陕西省土壤背景值,且Cd污染程度较高,Ni污染程度较低,而Cu、Cr、Mn基本不受污染。3个煤矿表层土壤各重金属元素质量分数均表现出污染区大于对照区,但这种变化幅度存在一定差异;Cu、Cr、Mn 3种重金属元素虽没有超出背景值,但已表现出一定程度的累积;煤矿周围土壤重金属污染受到开采年限、土壤质地、风向等因素的影响。3个煤矿污染区土壤剖面样品中,5种重金属元素质量分数基本上随着土壤深度的增加呈现降低的趋势,且这种趋势具有波动性。     

包气带不同深度土壤对甲苯和三氯乙烯的吸附研究

采用批实验研究了华北平原地下水中检出率较高的三氯乙烯和甲苯在沿污水河包气带不同深度土壤中的吸附情况。从3个地点分析结果来看,其中有机碳（OC）的质量分数均较低（最高为1.01%）。在河床和近河处土壤对甲苯和三氯乙烯的吸附总体上呈现出浅部土壤吸附性强的特点。在实验浓度范围内,土壤中无机矿物对有机污染物（特别是三氯乙烯）的表面吸附扮演了重要角色。土壤对甲苯的吸附表现出了强烈的非线性,而对三氯乙烯的吸附表现出了良好的线性关系。甲苯的吸附与土壤有机碳质量分数的关系要比三氯乙烯更密切,这说明了吸附作用过程与有机化合物的分子结构、疏水性等方面的性质也有关系。     

森林土壤对几种重金属污染的记忆效应

采用一定浓度(40～120 mg·L-1)Cd、Cr、Pb的氯化物溶液多次浇灌森林土壤,研究受以前污灌影响而导致某次污灌后土壤对重金属的吸持率下降的效应--记忆效应.结果表明土壤对Cr和Pb环境容量大,记忆效应不明显.多次浇灌CrCl3溶液后,土壤剖面20 cm以下采样点约99%的Cr被土壤吸持;3次浇灌PbCl2后各采样点Pb浓度下降率维持在85%以上,但污灌次数进一步增加,则土壤的吸持率下降.Cd的环境容量较小,增加投入会很快使土壤上层对其吸附达到饱和,吸附带随之下移,对地下水的安全构成威胁.     

几种萃取剂对土壤中重金属生物有效部分的萃取效果

采用6种萃取剂:pH=7的0.01mol/L CaCl_2、pH=7.3的0.005mol/L DTPA+0.1mol/L TEA(三乙醇胺)+0.01mol/L CaCl_2O.1mol/L NaNO_3、0.43mol/L HOAc、pH=7的0.05mol/L EDTA和pH=4.65的0.5mol/L NH_4OAc+0.02mol/L EDTA浸取液.对污染土壤中的重金属Cu、Zn、Cd、Pb、的进行了萃取,并比较了萃取剂的萃取能力。实验结果表明,HOAc、EDTA以及NH_4OAc-EDTA萃取各种重金属的能力远远大于其它几种萃取剂的萃取能力,是比较理想的萃取剂。     

Washing out heavy metals from contaminated soils from an iron and steel smelting site

Washing is a promising method for separating contaminants bound to the particles of soil ex-situ by chemical mobilization. Laboratory batch washing experiments were conducted using deionized water and varying concentrations of oxalic acid, citric acid, tartaric acid, acetic acid, hydrochloric acid and ethylenediaminetetra acetic acid (EDTA) to assess the efficiency of using these chemicals as washing agents and to clean up heavy metals from two heavily polluted soils from an iron and streel smelting site. The toxicity reduction index and remediation costs were analyzed, and the results showed that the soils were polluted with Cd, Pb and Zn. Hydrochloric acid and EDTA were more efficient than the other washing agents in the remediation of the test soils. The maximum total toxicity reduction index showed that 0.5 mol·L^-1 hydrochloric acid could achieve the remediation with the lowest costs.     

Sorption and leaching behavior of hexaconazole as influenced bysoilproperties

Sorption and leaching behavior of hexaconazole in four different soils (alluvial, red, laterite, and black) was studied using a batch equilibration technique. The values of the Freundlich adsorption constant 1/n_ads ranged from 0.75 to 0.85 for all four soils, showing strong non-linear behavior. Upon stepwise desorption with CaCl₂ solution (10 mmol·L^?1), release of hexaconazole was maximum with the first elution, the amount decreasing with each subsequent one. The leaching behavior under saturated flow conditions was also studied with soil columns packed in polythene tubes. The mobility of hexaconazole was maximum in sandy loam and minimum in black soil.     

Effects of eggshell addition on calcium-deficient acid soils contaminated with heavy metals

The eggshell was used to remediate the contaminated soil by heavy metals. The eggshell addition decreased the available state of the heavy metals. The available calcium in the soil increased due to eggshell addition. The efficiency was investigated in different moisture conditions. In this study, effects of water conditions (flooded, wet, or dry) and eggshell dosages (0, 0.1, 1.0, and 10.0 g/kg soil, respectively) on pH variation, content of unavailable state of heavy metals, form of heavy metals, and available nutritious element calcium (Ca) in acid soils contaminated with heavy metals were investigated, respectively. The soil samples were continuously cultivated indoors and analyzed by toxicity characteristic leaching procedure and community bureau of reference (BCR) sequential extraction procedure. The results showed that the addition of eggshell could effectively improve the pH of acid soil and increase it to neutral level. Moreover, the contents of unavailable state of heavy metals Cu, Zn, and Cd increased significantly. Furthermore, when the soil was cultivated under the flooded condition with 1.0 g/kg eggshell, the unavailable state of Cu, Zn, and Cd increased the most, and these heavy metals were transformed into residual state. On the other hand, the amount of available state of Ca increased to 432.19 from 73.34 mg/kg with the addition of 1.0 g/kg eggshell, which indicated that the addition of eggshell dramatically improved the available state of Ca. Therefore, eggshell could ameliorate the soil environment as it led to the decrease of available heavy metals and improvement of fertilization effectively. In a word, this study indicates that the addition of eggshell would be a new potential method for remediation of acid field soils contaminated with heavy metals.     

Investigation of correlativity between heavy metals concentration in indigenous plants and combined pollution soils

The accumulation of heavy metals (HMs) in soils is potentially hazardous to human, livestock and plant species. HMs in the combined pollution soils and indigenous plants were investigated in a non-ferrous metal-smelting area. The purpose of this study was to determine the HMs in the contaminated soil and different plant species found growing on it, as well as calculation of bioaccumulation coefficients (BACs). Representative sampling sites were identified according to the land-use types. A total of 12 surface soil samples and 32 plant samples were collected. HMs were analysed by inductively coupled plasma mass spectrometry. The levels of soil pollution were assessed using Nemerow’s synthetical contamination index method. The synthetical index was in the range of 16.81–198.11. This result indicated a heavy burden on local environment. HM concentrations in plants were directly related with soil concentrations. The average BACs of five metals were found in the order of Cd (0.309)?>?Zn (0.178)?≈?Pb (0.160)?>?Cu (0.105)?>?Sb (0.0672). Spontaneous weeds including Chenopodium album Linn, Kochia scoparia and trees of Leuce, Ulmus pumila were deemed HM accumulators. The results provided a practical basis for phytoremediation of HM-contaminated soils using accumulator species.     

溶解性有机物对土壤中重金属环境行为的影响

为揭示在溶解性有机物（DOM）作用下土壤中重金属的吸附和迁移规律并确定迁移数学模型,通过不同条件下的等温吸附实验和土柱淋滤实验,研究了溶解性有机物对重金属Cu,Cd,Pb,Zn在褐土中吸附和迁移行为的影响。结果表明DOM对Cu和Cd在土壤中的吸附促进作用较明显,对Pb有微弱的促进作用,对Zn的吸附影响不明显;随着pH的改变,25℃下Cu在土壤中的吸附高于15℃和35℃条件下。DOM质量浓度越高,Cd、Zn溶出的促进效果越明显,Cu、Pb则恰好相反。DOM对土壤中Cd、Zn的垂直迁移起着促进作用,而对Cu、Pb迁移起着一定的抑制作用;DOM对土壤重金属的平均迁移量随时间的延长而减少。此迁移模型能够定量计算并预测重金属质量浓度的时空分布。     

典型农耕区黑土和沼泽土团聚体颗粒中重金属的分布特征解析

了解重金属在土壤中的富集特征是其风险评价和土壤修复的基础。分别以黑龙江省典型的农耕黑土和沼泽土为研究对象,采用干筛法获得〉4000、4000～2000、2000～1000、1000～250、250～53和〈53衄16个粒级的土壤团聚体颗粒组。利用等离子质谱（ICP-MS）测定了本土和各级团聚体颗粒中Cr、Cd、As和Pb的含量,并对其颗粒组分布特征及对有机碳的响应进行了解析。研究表明,2种土壤中的重金属Cr、Cd和Pb的富集因子均大于1,而As则存在明显的流失。除了黑土中的As和Pb外,其他重金属随着团聚体粒径的增加而呈现富集减弱的趋势。其中,cr和cd主要趋向分布在粉．黏团聚体（〈53wn）颗粒中;Pb在黑土中易赋存于1000～2000μm大团聚体中,在沼泽土中则富集于53～250μm的微团聚体中;As不但趋向被吸附在53～250μm的微团聚体中,而且在黑土中也容易被吸附在〉l000μm的大团聚体中。金属质量负载计算表明,大粒径颗粒组对土壤中重金属含量的总体贡献较大。土壤中有机碳含量均随着团聚体粒径减小而升高,cr和Cd分布与颗粒有机碳含量正相关,黑土中As的分布与颗粒中有机碳含量负相关而在沼泽土中呈弱正相关,Pb的分布则与有机碳含量均无明显的相关性。     

土壤中镉的吸附解吸研究进展

首先概述了国内外关于土壤对镉的吸附解吸的基本研究方法与实验条件。用于吸附解吸实验的土样以通过20目筛为宜，而不同形式的支持电解质及其离子浓度的选择对实验结果有很大影响，应由实验的具体目的和要求确定合适的实验条件。位于土壤颗粒表面的各吸附点位与镉的结合能的能量高低不一，可将土壤对镉的吸附作用区分为专性吸附和非专性吸附。可用传统的或融入新参数的吸附等温线表达土壤对镉的吸附过程，土壤对镉的吸附性能可用综合因子来形容，如吸附势、吸持率、平均分配系数、Langmuir方程的常数k和Freundlich方程的系数k等表达方式，同时寻找这些综合因子与土壤基本理化性质之间的关系。文章最后讨论了影响吸附过程的主要环境因子，并就土壤pH和水分条件的影响机制进行了分析。     

污染土壤中有机质结合态重金属的研究

用物理与化学相结合的方法研究了2个污染土壤剖面中有机质结合重金属（Cd、Cu、Pb和Zn）的分布，把有机质相结合态重金属分为颗粒状有机质（POM）结合的重金属和与细土腐殖质结合的重金属。结果表明，土壤POM对重金属有明品的富集作用，其中〉2mmPOM重金属Cd、Cu、Pb和Zn的富集系数分别在1．4～3．2、2．5～2．6、2．8—3．9和3．0～3．9之间；而0．05～2mmPOM重金属Cd、Cu、Pb和Zn的富集系数分别在2．7～7．8、3．2～6．4、3．2～9．3和3．2～5．6之间，0．05～2mmPOM组分中重金属的平均富集高于〉2mmPOM组分。POM中重金属的富集程度与土壤重金属的积累呈正相关。有机质结合态重金属占土壤重金属总最的比例随土壤有机质积累而增高，表土层约40％以上的重金属以有机质结合态存在。     

土壤中铅的吸附-解吸行为研究进展

铅是重要的土壤重金属污染元素之一，了解铅在土壤中的物理化学行为，有利于预防和修复土壤的铅污染。土壤中铅的吸附-解吸行为，依吸附机理的不同，分为专性吸附和非专性吸附。土壤铅吸附的机理还存在不同的观点，如水解吸附／非水解吸附机理，单分子吸附／双分子吸附机理等。影响土壤中铅吸附-解吸行为的主要因素，有土壤矿物组成、土壤有机质、pH、温度、竞争离子等。文章最后对描述土壤铅吸附过程的主要数学方程(Langmuir方程、Freundlich方程和Temkin方程)作了论述。     

Sorption of heavy metals on organic and inorganic soil constituents

Sorption of heavy metals to organic matter and mineral soil constituents can hardly be separated experimentally. Here we studied the retention capacity of organic matter and minerals from soils in a long-term field experiment in which the organic carbon content had been altered, but the mineral phase had remained constant over time. The sorption of Cu, Cd and Zn showed a non-additive contribution of soil organic matter and minerals to the sorption capacity of soil. Sorption on organic matter exceeded mineral sorption from 6 to 13 times. This is the first time that sorption to soil organic matter is quantified in bulk soils.     

不同类型土壤对重金属的吸附特性

为了解重金属在土壤中的迁移转化规律,为确定土壤环境容量和治理土壤重金属污染提供理论依据,采用室内试验方法研究了采自山东的棕壤、黑龙江的黑土、陕西的黄棕壤和山西的褐土吸附Cu2 、Pb2 和Cd2 的特性及溶液pH、外加腐殖酸、溶液中重金属初始含量对吸附的影响.由振荡平衡法进行吸附试验,原子吸收分光光度法测定平衡溶液中重金属的吸光度值.试验结果表明:随着溶液中Cu2 、Pb2 和Cd2 含量的增大,4种土壤对Cu2 、Pb2 和Cd2 的吸附量逐渐增大.溶液pH值对土壤吸附重金属的影响因土壤性质和重金属特性的不同而不同.加入腐殖酸,4种土壤对Cu2 、Pb2 和Cd2 的吸附量明显减少.不同吸附模型拟合结果表明,4种土壤对Pb2 的吸附等温线都符合 Langmuir 方程和Freundlich方程,对Cu2 吸附等温线拟合的Langmuir 方程和Freundlich方程的相关性不理想,对Cd2 吸附等温线拟合符合Freundlich方程.     

土壤与沉积物对多环芳烃类有机物的吸附作用

吸附作用是疏水性有机物在土壤和沉积物环境中的重要迁移转化行为之一。多环芳烃是环境中一种重要的疏水性有机污染物。文章着重阐述了多环芳烃类有机物在土壤和沉积物中有机质和粘土矿物吸附机理，指出土壤、沉积物有机质的结构异质性是导致非线形吸附的重要原因；分析了影响多环芳烃吸附过程的诸多因素，并提出该研究领域存在的问题以及今后发展的方向。     

Effect of acid rain on the fractionation of heavy metals and major elements in contaminated soils

Acid rain is a serious environmental problem worldwide. In the present study, we investigated the effect of acid rain (1:1 equivalent basis H₂SO₄:HNO₃) at pH values of 2.0, 4.0 and 7.0 on the fractionation of heavy metals (Cd, Cu, Fe, Mn, Ni, Pb and Zn) and major elements (K, Na, Ca, and Mg) in contaminated calcareous soils over a 2084 h period. Heavy metals and major elements in soil samples were fractionated before and after 2084 h kinetic release using a sequential extraction procedure. Before kinetic studies the predominant fractions of K, Na, Ca, Mg, Cd and Ni were mainly associated with carbonate fraction (CARB), whereas Fe, Mn and Zn were associated with the Fe–Mn oxide fraction (Fe–Mn oxide). The highest percentage of Pb and Cu were found in the exchangeable (EXC) and organic matter (OM) fractions, respectively. After kinetic study using different simulated acid rain solutions, the major fractions of heavy metals (expect of Cu) and Na was the same as before release. Upon the application of different acid rain solutions, K and Mg were found dominantly in Fe–Mn oxide fraction, whereas Ca was in the EXC fraction. The results provide valuable information regarding metal mobility and indicated that speciation of metals (Cu and Zn) and major elements in contaminated calcareous soils can be affected by acid rain.     

杭州市郊蔬菜地土壤重金属环境质量评价

对杭州市郊4个主要蔬菜基地的土壤中的重金属铅、锌、铜含量进行测定分析,利用不同的评价方法和标准来评价杭州市郊蔬菜地土壤重金属的环境质量状况。结果发现如以自然背景值为评价标准,则蔬菜基地土壤中的重金属超过污染指标,污染程度为Pb > Cu > Zn;如以国家《土壤重金属污染评价标准》为评价标准,则蔬菜基地土壤中的重金属未超过污染指标,污染程度为Zn > Cu > Pb;在4个调查区中,拱墅区土壤重金属大于其它3个区。