Lecture 3

Methods to study and test sorption and

leachability

• Sorption – from SWP1

• Percolation tests
• Extraction tests
• Key factors
• OECD test
• Example
Sorption - methodology

Sorption- revisited from SWP1

Physisorption
Partitioning

Ion exchange Chemisorption

Surface complexation
(Ad)sorption
Hydrophobic sorption Physisorption
Sorption
(Precipitation)

(Uptake into biological tissue)

• Characterisation of sorption  sorption isotherms (incl. desorption) + kinetics

• How to study?  batch (shaking flasks) or column/chromatography (leaching)
• Main use: In models – either equilbrium (e.g. MINTEQ) or dynamic (time is a
variable)
Sorption - methodology

Sorption- revisited from SWP1 土壤中的吸附剂有哪些？

： SOM（阳离子交换、分配）
3（4）大类

粘土硅酸盐（阳离子交换、表面络合
、疏水吸附）
Which are the sorbents in soil?  3 (4) major classes: 金属（Fe、Mn、Al氧化物）（表面
 SOM (cation exchange, partitioning) 络合、阴离子交换
） 方解石（表面络合，“沉淀”）
 Clay silicates (cation exchange, surface complexation, hydrophobic sorption)
 Metal (Fe, Mn, Al oxides) ( surface complexation, anion exchange)
 Calcite (surface complexation, “precipitation”)

How do we determine the contents of the sorbents? 我们如何确定吸附剂的含量？ SOM（

包括炭黑）：总碳，点火
 SOM (incl. carbon black):Total C, ignition 粘土：粒度分布，XRD
 Clays: Particle size distribution, XRD 金属氧化物：萃取（草酸盐，CBD）
方解石（碳酸盐测定）
 Metal oxides: Extraction (oxalate, CBD)
 Calcite (carbonate determination)
重要的吸附剂特性：
物理：尺寸、形态、比表面积
Important sorbent characteristics: 化学：组成、浓度、键合位点、键合
强度、pKa 值 (PZC)、疏水性
 Physical: size, morphology, specific surface area
 Chemical: composition, concentration, bonding sites, bonding strength, pKa values
(PZC), hydrophobicity

Distribution in soils: horizons and macropores

Sorption - methodology

Sorption- revisited from SWP1

The soil as a chromatographic

column. Dispersion, adsorption
and degradation controls the
solution at the outlet of the
“column”. 土壤作为色谱柱。分散、吸附和降解
控制着“柱”出口处的溶液。
The soil water

Typical soil solution sampling devices

Zero-tension Lysimeter Tension cup lysimeters Centrifugation

 Desorption and leaching
test types
Most existing soil leaching and extraction tests belongs to one of
the following groups:
大多数现有的土壤浸出和提取试验属
于以下组之一： 渗滤试验：
Percolation tests: - 柱浸出试验
- Column leaching tests - 蒸渗仪浸出试验
- Lysimeter leaching tests

Extraction or batch tests: 提取或批量测试：

- Single batch extraction/leaching tests - 单批次提取/浸出测试
- 多批次提取/浸出测试
- Multiple batch extraction/leaching tests - pH 静态浸出测试
- pH-static leaching test - 可用性测试
- Availability test - 特殊提取和顺序化学提取

- Special extractions and sequential chemical extractions

Special tank tests: testing of diffusion driven leaching from monolithic waste.
This type of test may be used for compacted soil and waste but will not be
further addressed in this course since the interpretation is based upon
different principles (non-equilibrium conditions) than the more commonly
used tests.
 Column leaching tests and
the L/S concept
土壤材料的垂直柱
上流或下流
收集并分析
• vertical column of the soil material 模拟雨水渗滤 与自然条件相比加速
• upflow or downflow 流速 假设（局部）接近平衡/稳态 通
• collected in fractions and analysed 常持续数周至数月 对应于 L/S = 0.0 - 0.
1 l/kg 或更低的分数可能非常适合 L/S
• simulates rainwater percolation = 0 - 2 l/kg（甚至 L/S = 10 l/kg）
• accelerated flow rate compared to natural conditions
• assumption of (local) near-equilibrium/steady state
• duration of typically several weeks to several months
• fractions corresponding to L/S = 0.0 - 0.1 l/kg or even lower
may well suited for L/S = 0 - 2 l/kg (even L/S = 10 l/kg)
Extraction or batch leaching tests

Multitude of purposes:
• availability of various components for various purposes under
various conditions 提取或分批浸出试验 多种用途： 各种
成分在各种条件下用于各种目的的可
• simulations (crude) of actual leaching behaviour 用性
• instead of/conjunction with column leaching tests. 实际浸出行为的模拟（粗略）
代替/与柱浸出试验结合。
The steps:
• a certain amount of soil is brought into contact with a leachant
in a closed or open vessel and agitated for a certain period of
time
• liquid and solid phases subsequently separated
• the liquid is analysed for the parameters of interest.
• contact times few hours - few days
• single batch leaching test at a specified L/S ratio (min 2 l/kg)
• high L/S values - analytical detection problems? 步骤： 将一定量的土壤与密闭或敞开
• standardised batch leaching tests L/S 2 - 20 l/kg. 容器中的浸出剂接触并搅拌一定时间
随后分离液相和固相 分析液体的相关
参数。

接触时间数小时至数天 在指定的L/S
比（最小2 l/kg）下进行单批次浸出测
试 高L/S 值- 分析检测问题？ 标准化
批量浸出测试 L/S 2 - 20 l/kg。
Sorption - methodology

Sorption- methodology
OECD guideline 106

Objective: Evalute the sorption of a chemical (organic chemicals mainly!!) on different

soil types (sorbents, pH)

Three steps (tiers): 目标：评估化学品（主要是有机化学

品！！）在不同土壤类型（吸附剂、p
Tier 1: solid-solution ratio H）上的吸附 三个步骤（层级）：第
1 层：方法人工制品和吸附稳定性的
equilibration time 固溶比平衡时间测试 第 2 层：不同土
test of methodological artefacts and sorbate stability 壤类型吸附动力学单点测定 Kd 第 3 层
：吸附等温线和 Freundlich 拟合解吸
Tier 2: different soil types
adsorption kinetics
single-point determination of Kd
Tier 3: adsorption isotherms and Freundlich fitting
desorption

Direct or indirect determination of sorption: When should we use one or the other
method? (weak/strong adsorption, instability, sorption to equipment)
Sorption - methodology

Where can it go wrong?

• Too high liquid to solid ratio  too little sorption  too high error in sorbed mass

• Sorbate is unstable 液固比太高 吸附太少 吸附质量误差

太大
山梨酸盐不稳定 山梨酸盐吸附到设
• Sorbate sorbs to the equipment 备上 分析方法：土壤中溶质的干扰
山梨酸盐不溶于水或溶解度很小

• Analytical method: Interference from solutes in the soil

• Sorbate is not soluble in water or has very little solubility

Extraction or batch leaching tests
pH-static and availability tests

• pH-static leaching tests – input to hydrogeochemical models.

• availability tests, high L/S ratios (typically 50 to 200 l/kg), finely
ground soil material (typical grain size < 100 - 200 m), pH-static
conditions (1-2 pH values), favouring the solubility.
• some regulatory tests, availability = application of aggressive
leachants containing acids or complexing agents (e.g. carbonic
acid/CO2, acetic acid, ammonium acetate, EDTA, citric acid).
• Special extractions, sequential extraction procedures (e.g. Tessier
et al., 1979), specific aspects , association of leachable 提取或分批浸出测试 pH 静态和可用
性测试 pH 静态浸出测试——输入水
components with various mineral phases. 文地球化学模型。

可用性测试、高 L/S 比（通常为 50 至

200 l/kg）、精细研磨的土壤材料（典
型粒度 < 100 - 200 洀淿 、pH 静态条件
（1-2 pH 值），有利于溶解度.

一些监管测试，可用性 = 使用含有酸
或络合剂（例如碳酸/CO2、乙酸、乙
酸铵、EDTA、柠檬酸）的侵蚀性浸出
剂。

特殊提取、顺序提取程序（例如 Tessi
er 等人，1979 年）、特定方面、可浸
出成分与各种矿物相的关联。
 Key factors

• particle size and homogeneity of the sample

• mode of contact between liquid phase and sample material
contact/agitation time, pH (and buffering capacity)
• contact with the atmosphere
• redox conditions of the leaching system
• composition of the leachant.

Other key issue:

to define the background leaching or release of contaminants from
soils considered “uncontaminated” and to define safe levels of
release as part of the setting of risk-related limit values for testing
of the leachability of soil
样品的粒度和均匀性 液相和样品材料
之间的接触方式 接触/搅拌时间、pH
（和缓冲能力） 与大气的接触 浸出
系统的氧化还原条件 浸出剂的组成。

其他关键问题：定义被认为“未受污
染”的土壤中污染物的背景浸出或释
放，并定义安全释放水平，作为与风
险相关的限值设置的一部分，用于测
试土壤的可浸出性
 Example:
Composition of leachant
Results of filtration test involving two soil samples.

Filtration time, sec.

Ca(NO3)2 concentration
Pb-sample* As-sample**
0M 260 >10000
0.001 M 9 8
0.002 M 7 6
0.005 M 6 5
0.010 M 6 5
*Pb-sample: Pb-contaminated clay-loam soil
**As-sample: As-contaminated sandy soil

Hjelmar et al. (2000)

 Example:
Background concentrations of
inorganic soil contaminants

The soil samples were collected from rural areas (both agricultural and forest soils) as
well as urban areas. Their pH values range from 3.5 to 7.7, and the texture varies from
sandy soils to soils containing more than 20 percent (w/w) clay (i.e. particles < 0.002
mm). All the
 Example:
Results of batch leaching tests on
10 unpolluted soils.

The tests were performed at L/S = 2 l/kg using a 0.001 M CaCl2 solution