Preface

Persistent Organic Pollutants commonly known as POPs are believed to be dangerous for humans, animals and ecosystem. These chemical compounds, especially the pesticides persist in the environment for longer durations up to decades. They are believed to bio-accumulate through the food web and exposure to these chemical compounds can lead to deadly diseases such as cancers and eventually death. International community has adopted the Stockholm Convention to address the issues related to these persistent organic pollutants. These chemicals were introduced in Pakistan in 1954 and used primarily for malaria control until the Pesticides Ordinance that came in to force in 1973. It is estimated that 6083 metric tons of these unused Persistent Organic Pollutants (POPs) – pesticides are stored at various locations across Pakistan and still posing threat to humans. It is important to identify these pesticides and dispose-off in environmentally sound manner. For this purpose the relevant departments, laboratories and workers need capacity building in identification, handling and disposal of POPs pesticides. Training programs based on a curriculum and training manual covering all the subjects of relevance in accordance with Stockholm Convention are an important step in final disposal of POPs pesticides.

The purpose of the training manual is to give schematic teaching assistance to the Trainer to effectively impart training to improve the capacity and necessary skills of the trainees on Handling and Management of the Persistent Organic Pollutants (POPs) with particular reference to Pesticides.

The training manual is designed in a way that trainer can easily adopt him/herself according to the needs of the trainees. The teaching points are mentioned in PowerPoint slides and descriptive and supportive text is provided below each slide. Thus enough details and description of terms has been provided and trainees could easily find answers to their possible questions.

The training manual has been divided into modules. Each module reflects the topics necessary to learn and understand a wider scope topic and its allied disciplines. Assessment of learning efficiency of trainees has been given due importance in this manual. As such exercises have been given at the end of each manual so that trainer can easily assess the absorption of knowledge by the trainees. Trainer is required to provide answer sheets to each trainee at the end of each module.

The trainer is expected to give enough time to trainees for interactive discussions and posing any related questions. Site visits such as visit to laboratory and POPs storage site would be beneficial for trainees to understand the problem in its true essence.

The most important feature of the training manual is that it is designed in such a way it can be used for training a wide variety of trainees such as for Higher Management responsible for decision making, Laboratory staff, Civil Society representatives, Academia, Research Organizations, workers responsible for handling of POPs, etc. The trainer can easily utilize the relevant portions for each type of trainees.

This manual has been developed on the basis of the curriculum on POPs pesticides developed recently. A number of documents and online resources were also consulted. This included the text of Stockholm Convention, Basel Convention, UNEP guidebooks, UNDP POPs project documents and research papers of the scholars. Necessary citation has been given at relevant places according to internationally accepted standard methodology.

1

The author acknowledges the technical knowledge sharing by the UNDP and POPs project stakeholders. The technical facilitation by UNDP POPs project staff and colleagues remained very instrumental in finalization of this manual.

Sardar Ahsan Younus, PhD

2

ContentsTitle Page

No.

Module 1: Introduction to POPs and Stockholm ConventionExercise

Module 2: Health Effects of POPsExercise

Module 3: Sampling and Testing for POPsExercise on SamplingExercise on customized datasheet

Module 4: Analyses of POPsExercise

Module 5: International Standard Methods for POPs analyses

Module 6: Field Handling of POPs Contaminated EquipmentExercise

Module 7: Disposal of POPs materialsExercise

Module 8: Health and SafetyExercise

311

1115

153035

3761

61

6674

74105

105110

3

4

Persistent Organic Pollutants, commonly known as POPs are chemicals with high toxicity originated through anthropogenic activities. Due to their high toxic nature POPs are believed to cause a variety of negative impacts on living organisms including humans. Particularly in humans POPs can cause birth defects, severe diseases and death1. POPs resist photolytic, biological or chemical degradation, leading to their bioaccumulation in the food chain. They can be transported over long distances in the atmosphere, resulting in widespread distribution across the earth including regions where they have never been used. Owing to their toxic characteristics, they can pose a threat to humans and the environment.

Usually Persistent Organic Pollutants (POPs) are organic chemicals containing carbon and hydrogen and characterized by adverse effects on life, bioaccumulation, persistence and long range transport.

A number of POPs are produced intentionally, such as those used as pesticides or used in industrial processes, while others are generated unintentionally as by-products of various industrial or combustion processes. At present there are twenty six chemicals that have been proved to have POPs characteristics and are designated for elimination or emission reduction. They are composed of: intentionally produced pesticides; some industrial chemicals, which are Polychlorinated Biphenyls and Hexachlorobenzene; plus the unintentionally produced emissions of certain industrial and combustion processes.

1 National Implementation Plan for Phasing Out and Elimination of POPs from Pakistan,

5

Owing to their nature and properties POPs present unique challenge as they persist in the environment, bio-accumulate in fatty tissues of living organisms and pose risks of adverse effects to human health and the environment. Their long-range transport has been recognized as an important factor affecting ecosystems and human populations across the globe.

Recognizing the sustaining of harmony between species in the ecosystem and peaceful living conditions the international community has called for urgent global action to reduce and ultimately eliminate the initial 12 chemicals that have been found to be the most dangerous to health and the environment.

POPs possess a particular combination of physical and chemical properties2. Once released into the environment, they:

remain intact for exceptionally long periods of time (up to many years); become widely distributed throughout the environment as a result of natural

processes involving soil, water and, most notably, air; accumulate in the fatty tissue of living organisms including humans, and are found at

higher concentrations at higher levels in the food chain; and are toxic to both humans and wildlife.

2 The Stockholm Convention, http://chm.pops.int/TheConvention/ThePOPs/tabid/673/Default.aspx

6

Bioaccumulation is a process in which POPs enter bodies of the living organisms and stay there for longer durations causing health problems. POPs are usually not soluble in water but POPs are readily absorbed in fatty tissue, where concentrations can become magnified by up to 70,000 times the background levels. Fish, predatory birds, mammals, and humans are high up the food chain and so absorb the greatest concentrations. When they travel, the POPs travel with them. As a result of these two processes, POPs can be found in people and animals living in regions such as the Arctic, thousands of kilometers from any major POPs source.

7

Protecting humans from dangerous effects of POPs is an international issue for which international community has to jointly work for common goals. The Stockholm Convention on POPs is an international treaty among countries aimed at protecting human health and the environment from POPs. The Stockholm Convention is designed to commit governments to proceed towards control and bans on the production, generation and use of a harmful group of pesticides and industrial chemicals and emissions of unintended by-products and promotes and requires appropriate substitution with cleaner products, materials, processes, and practices. It will likewise ensure the environmentally sound management and disposal of POPs waste. (See Annex I for the Stockholm Convention)

After designing and deliberating on the various components of the convention, the Stockholm Convention was adopted in May 2001. This Convention contains strong provisions to reduce and eliminate releases of POPs to the environment. Among other things, the Convention aims to eliminate the production, use of POPs chemicals, that have been intentionally produced; to identify and remove of Polychlorinated biphenyls (PCBs) from use; to restrict DDT use to disease vector control in accordance to WHO guidelines; to minimize and where possible, ultimately eliminate those POPs formed as unintentional by-products and to eliminate releases of POPs from stockpiles and wastes.

Affirming the dangers posed by POPs the Convention also calls for ceasing the production and use of new pesticides and industrial chemicals that have characteristics of POPs. The Convention establishes a register of specific exemptions for permitted production and use of POP Pesticides as well as acceptable use of DDT. It also provides the framework to expand the scientific monitoring of POPs levels in the environment.

8

After adopted in May 2001, the Stockholm Convention on POPs entered into force in May 2004. The objective of the Convention is to protect human health and the environment from persistent organic pollutants starting with an initial list of 12 chemicals namely, Aldrin, Dieldrin, DDT, Endrin, Chlordane, Hexachlorobenzene, Mirex, Toxaphene, Heptachlor, Polychlorinated Biphenyls (PCBs), Polychlorinated dibenzodioxins (PCDDs) and Polychlorinated dibenzofurans (PCDFs). Later on new chemicals have also been added in to the list of POPs.

Aldrin (Listed under Annex A)Chlordane (Listed under Annex A)DDT (Listed under Annex B with acceptable purpose for disease vector control)Dieldrin (Listed under Annex A)Endrin (Listed under Annex A)Heptachlor (Listed under Annex A)Hexachlorobenzene (HCB) (Listed under Annex A and Annex C)Mirex (Listed under Annex A)Toxaphene (Listed under Annex A)Polychlorinated biphenyls (PCB) (Listed under Annex A with specific exemptions and under Annex C)Polychlorinated dibenzo-p-dioxins (PCDD) (Listed under Annex C)Polychlorinated dibenzofurans (PCDF) (Listed under Annex C)

9

At its fourth meeting held from 4 to 8 May 2009, the Conference of the Parties adopted amendments to Annexes A, B and C to the Stockholm Convention to list nine new persistent organic pollutants (SC-4/10-SC-4/18). Pursuant to paragraph 4 of Article 21 of the Convention, the amendments were communicated by the depositary to all Parties on 26 August 2009.

10

Any Party may submit proposal for listing a new chemical in Annex A, B, or C of the Convention. The POPs Review Committee evaluates the proposals and makes recommendation to the Conference of the Parties on such listing in accordance with Article 8 of the Convention. Currently, the following chemicals are under review.

11

12

Persistent organic pollutants especially the pesticides are known for their carcinogenic properties. The link between POPs pesticides and cancers has been a concern. These POPs pesticides may cause developmental defects, chronic illnesses, cancers and death. These chemicals not only effect humans but they also affect plants and animal species and natural ecosystems negatively in close proximity and even at a significant distance away from the original source of exposure.

At present the normal daily food supplies in most regions of the world, especially fish, meat and dairy products, are suspected to be contaminated by POPs. Both people and wildlife everywhere in the world, carry burdens of POPs at near levels that can cause injury to human health and to entire ecosystems.

The implications of chronic and acute exposure to POPs are not fully understood. Laboratory investigations and environmental impact studies in the natural environment have indicated that POPs exposure can result in endocrine disruption, reproductive and immune dysfunction, brain and nervous system disorders, developmental disorders and cancer. Some organochlorine chemicals are likely carcinogenic by promoting the formation of tumors, PCBs are classified as probably carcinogenic to humans, while an additional eight of the 12 other POPs identified in the Stockholm Convention are classified as possibly carcinogenic to humans. The remaining three - endrin, dieldrin and aldrin are classified by WHO as highly hazardous (class 1b) on the basis of their acute toxicity to experimental animals.

13

A number of POPs have been associated with cancers and tumors at multiple sites; neuro-behavioural impairment including learning disorders; immune system changes; reproductive deficits of exposed individuals as well as their offsprings; and disease such as endometriosis, increased incidence of diabetes and others.

POPs are associated with serious human health problems, including cancer, neurological damage, birth defects, sterility, and immune system defects.  Laboratory studies have shown that low doses of certain POPs can adversely affect organ systems.  Chronic exposure to low doses of certain POPs may affect the immune and reproductive systems.  Exposure to high levels of certain POPs can cause serious health effects or death.  In addition, studies have linked POP exposure to diseases and abnormalities in a number of wildlife species, including various species of fish, birds, and mammals.  For example, in certain birds of prey, high levels of DDT caused eggshells to thin to the point that the eggs could not produce live offspring.

14

15

16

Sampling can be done for two types of laboratory tests which are identification of type of chemical at a stockpile and identification of type and concentration of a chemical in a matrix. In any case the objective of sampling activity is to obtain a sample that can serve the objective of the study commissioned (UNEP, 2007). In this activity it is considered indispensable to ensure the representativeness and integrity of the sample during the whole sampling process.

Additionally, quality requirements in terms of equipment, transportation, standardization, and traceability are indispensable. It is important that all sampling procedures are agreed upon and documented before starting a sampling campaign.

The analyte (i.e. the POPs of interest), matrix, sampling site, time or frequency, and conditions should be determined depending on the objective of the sampling.

17

Obtaining a sample of the matrix of interest is an often-overlooked but vital component of any environmental monitoring program. Failure to properly collect a sample can invalidate any results subsequently obtained. The sample should be representative of the original environmental matrix (air, water, sediment, biota, etc.) and be free of any contamination arising during sample collection and transport to the analytical facility. The collection of a representative sample starts in the office or laboratory with the training of personnel and formulation of a sampling plan, moves to the field for the actual sampling, and ends with the shipment of the sample to the laboratory.

A successful sampling strategy must begin with a thorough plan and established protocols. Areas of questions which need to be addressed while planning the sampling trip include: 1) selection of the sampling method to obtain a representative sample, 2) determination of the sample quantity needed to meet the minimum quantitation limits of the analytical method, 3) identification of quality control (QC) measures to be taken to address any bias introduced by the sample collection, 4) identification of safety measures that need to be taken, and 5) determination of sampling objectives. The study plan must define the chemicals to be assayed in the sample and sample size requirements of the analytical methods. Different extraction and processing procedures may be needed to isolate targeted chemical classes from each other and potential interferences, resulting in larger sample size requirements. If sample size is limited, then alterations to the processing methods or changes to the overall study design may need to be made. If possible, reconnaissance trips to sampling sites will greatly aid in the determination of the logistical needs of the sampling plan.

Documentation of the sampling trip is critical as observations and measurements made in the field are often necessary for the integrity of the sample and can be instrumental in the final interpretation of the chemical analyses. Depending on the study design and properties of the targeted chemicals, water quality parameters such as temperature, flow, pH, turbidity, etc., may need to be taken. The field log should include sample collection procedures, location of the sampling sites on maps, global positioning system (GPS) coordinates or other data to identify the site(s), date

18

and time samples were collected, types of QC that were used, and names of the personnel involved in the sample collection.

19

The sample collection plan becomes a balancing game between the numbers of samples which can be taken, defined by sample availability and funding, and the amount of uncertainty that can be tolerated by the study objectives. When collecting samples, regardless of the matrix, the amount of uncertainty associated with the sampling decreases with increasing number of samples. Sample collection can follow a judgmental, systematic, or random pattern approach (Keith, 1991; Radtke, 2005). A judgmental approach focuses the sampling points around a predetermined spot such as a known point source. A systematic approach involves taking samples from locations identified by a consistent grid pattern. The random approach has no defined locations for sample collection and requires a high number of samples to be taken, but generally results in the lowest uncertainty.

20

Regardless of the type of sample matrix method used, issues of sample preservation, storage conditions and time, and shipping methods must be resolved. Samples should be collected with equipment made of stainless steel, aluminum, glass, or fluorocarbon polymers. Materials made of polyethylene, rubber, or other plastics should be avoided due to the potential for these materials to absorb or desorb targeted chemicals from/into the collected sample. Since plasticizers and flame retardants are commonly targeted ECs, plastics should not be used as they may contain high levels of these chemicals from the manufacturing process. The need for sample preservation, which can vary among chemical classes, often requires the addition of chemicals to water samples, but this is generally not recommended for most ECs. If elevated levels of residual chlorine are present in a water sample, sodium thiosulfate is often added to prevent the formation of chlorinated by-products (Keith, 1991; US Environmental Protection Agency, 2007a, 2007b). To prevent alteration, samples are shipped chilled (<4-6 °C) via overnight carrier to the laboratory and if ECs are potentially sensitive to UV radiation, amber bottles are used to prevent photo-degradation.

21

22

With respect to sampling indispensable requirements include:

Equipment: To have adequate sampling instruments according to the type of matrix and POP (dredger, HiVol, water bottles, etc.);

Materials: Sampling instrumentation that is analyte-compatible, including utensils, containers, etc. (stainless steel-glass, never plastic);

Personal protection: Those in charge of the sampling must wear adequate protection outfits depending on the type of samples they will work with (gloves, rubber boots, goggles, etc.);

Sample blanks: These allow for the assessment of potential contamination; Preservation: Samples and sample blanks will be preserved according to matrix

and type of POP requirements; Transportation: Adequate transportation that minimizes the possibility to

contaminate the sample, ensuring its integrity and conservation until it reaches de laboratory in charge of the analysis;

Availability of “in situ” monitoring equipment: To measure relevant environmental parameters according to each environment. The environmental conditions should be registered;

Geo-referencing and photographic registers: Availability of GPS to locate sampling sites with precision and ensure future location of the site;

Standardized protocol: Well-established sampling procedures have to be applied. Such sampling protocols have been developed by institutions or organizations such as ASTM (American Society for Testing and Materials), EC (European Commission), US-EPA (Environmental Protection Agency), GEMS (Global Environment Monitoring System), WHO (World Health Organisation);

23

Key considerations include:

Unambiguous labels are needed; Interface between sampling personnel and analytical laboratory: Close

cooperation is crucial between project planners, the samplers, the analytical laboratory, and data users;

Training of personnel: Personnel should be sufficiently trained and familiarized with the sampling techniques. An ecosystem expert is needed in the sampling group and some local people could act as guides;

Storage capacity: The laboratory must have an adequate storage capacity, i.e., refrigerators or freezers at sufficiently low and stable temperatures, to ensure the integrity of the samples. These temperatures should be monitored constantly and documented.

Waste Treatment: Consideration of suitable treatment/handling of the waste generated during the sampling.

24

A Standard Operating Procedure (SOP) has to be established for each type of matrix (several similar matrices can be combined). In these SOPs the following requirements must be addressed:

The objective of the sampling exercise, including sampling protocols and specifications;

Sample size in accordance with the analytical requirements and limitations in order to meet regulations or other objectives as given in the study;

Description and geographic location of the sampling sites, preferentially with GPS coordinates;

Guidelines for representative samples; Criteria for composite samples, e.g., number of sub-samples, homogenization; Date, time of the sample taking; Conditions during sampling; Time intervals between sampling exercises; Specifications for the sampling equipment, including the operating, maintenance,

and cleaning procedures; Identity of the person who has taken the sample; Full description of sample characteristics; Labeling of samples (in the field) and sample registration for further follow-up; Indication of expected level of POP concentration in the sample; Any additional observation that may assist in the interpretation of the results; Quality assurance procedures to prevent cross-contamination.

The SOP should also contain a section with details on personal protective equipment that must be worn and listing of other safety concerns as appropriate.

25

Water is an extremely heterogeneous matrix both spatially and temporally (Keith, 1990). The mixing and distribution of waterborne chemicals in a water body are controlled by the hydrodynamics of the water, the sorption partition coefficients of the chemicals, and the amount of organic matter (suspended sediment, colloids, and dissolved organic carbon) present. Stratification due to changes in temperature, water movement, and water composition can occur in lakes and oceans resulting in dramatic changes in chemical concentrations with depth (Keith, 1990). Because episodic events from surface runoff, spills, and other point source contamination can result in isolated and/or short-lived chemical pulses in the water, sampling sites and methods must be carefully selected.

Time-weighted average (TWA) concentrations of chemicals are commonly used to determine exposure, they are a fundamental part of an ecological risk assessment process for chemical stressors (Huckins et al., 2006). Since grab samples only represent the concentration of chemicals at the instant of sampling, TWA exposure is difficult to accurately estimate even with repetitive sampling.

A wide range of water collection methodology has been employed for obtaining samples for POPs analysis, ranging from hand dipping of 1L bottles to in situ submersible samplers collecting hundreds of liters. It is difficult to give general recommendations as they will depend significantly on study objectives and local capacity. Standard operating procedures for selecting sites, cleaning equipment, and avoiding contamination, e.g. by use of “clean hands/dirty hands” protocols are available from USGS (2006) with a focus on rivers and streams. The European Commission (2007) and ISO (2006) provide practical guidance for sampling of contaminants in freshwaters.

26

Sampling depths in the range of 1 to 10 m are recommended. This is a practical range of depth based on use of ship intakes and on-board pumping systems. Niskin or Glo-flo type samplers can be used for deeper depths, and depth profiles, however, there is potential for wall effects (contamination, sorption) particularly with small volumes (Wells 1994; Petrick et al. 1996). Adsorption losses can be evaluated using spikes of surrogates added to sample containers or to oceanographic bottles once they have been brought to the surface. Actual depths will depend on the characteristics of the water body. Care should be taken to avoid sampling the surface micro layer because it could have higher levels of contamination due to the presence of particulates, lipids and hydrocarbons (Wurl et al 2006).

Assuming sampling of background sites is the main goal of a Groundwater Monitoring Plan (GMP) for water, then the number of sampling techniques that can realistically be applied in order to achieve adequate limits of detection above blanks is limited. The techniques available are either (1) pumping water through solid phase media (C18 disks or columns, XAD resin, or polyurethane foam or (2) passive sampling with SPMDs (Semi-permeable membrane device), silicon rubber or polyethylene plastic sheets. A major exception is in sampling for PFOS.

27

Direct pumping thru a filter into a column holding the solid phase media has been widely employed in studies of POPs including HCH isomers in remote lake and ocean waters. There are many variations of this including the use of in situ samplers which are programmed to turn on and off underwater, and in line systems bringing seawater directly into clean rooms on ships. There have been several recent investigations of the performance of various solid phase media for extracting hydrophobic organics from surface waters. A multi-investigator study led by the European Commission Joint Research Centre (ECJRC) showed that PBDEs and PAHs could be determined adequately in natural water by a wide range of sampling and analytical methods. A key issue identified in the ECJRC study was partitioning between particles suspended in the water body. The recommendation from this latter study, and in European guidance (European Commission 2007) was to separate suspended particulate matter (SPM) from the water using appropriate filtration so that a “so-called” dissolved phase, operationally defined as contaminant that passes a 0.7-1 μm glass fiber filter (GFF), was analysed separately.

Solid-phase extraction (SPE) cartridges have been widely used to extract relatively small volumes (1–5 L) for OCP analysis. They also have the advantage of being performed in the field with simple portable pumping equipment (Zuagg et al. 1995) and other media such as divinylbenzene solid-phase disks have been shown to outperform XAD resins for OCP and PCB extractions of filtered water (Usenko et al. 2005).

28

PFOS and related perfluoroalkyl compounds (PFCs) are water soluble and have relatively low sediment-organic carbon partition coefficients compared to neutral halogenated compounds on the POPs list. Thus the PFCs are preferentially found in the dissolved phase in surface and ground waters.

PFOS and other PFCs are readily detected in all surface waters at (Picogram per liter to nanogram per liter) pg/L to ng/L. There have already been a large number of surveys of PFOS and other PFCs in rivers as well as measurements in all the major world oceans (Yamashita et al. 2008; Ahrens et al. 2009a). Collection of seawater samples has been done through ship intake systems (Ahrens et al. 2009a) and via Niskin bottles (Yamashita et al. 2004) into plastic or glass bottles. In lakes and large rivers, direct pumping into sampling bottles (Furdui et al. 2008) and collection from Niskin type samplers (Scott et al. 2009; Scott et al. 2010) and from ship intakes (Ahrens et al. 2009b) has been used. Samples for PFOS analysis have generally not been filtered prior to extraction. A recent study of waters in the Elbe River (Germany) and the North Sea indicated that on average 14% of PFOS was in the particulate phase (Ahrens et al. 2009b). In ocean waters PFOS was not detectable on particulates (Ahrens et al. 2009a) likely because of the lower SPM and thus filtration is not recommended, unless it can be done with an inline system or in a clean room (Ahrens et al. 2009b) because it could introduce contamination. Contamination is also introduced from polytetrafluoroethylene (PTFE) materials due to the use of perfluoroctanoate as a processing aid for PTFE production. Common sources are PTFE tubing, o-rings and other seals. PTFE bottles or bottles with fluorinated interior coatings and these should be avoided.

29

Stuer-Lauridsen (2005), Vrana et al. (2005) and Booij (2009) have thoroughly reviewed the history and use of passive samplers in POPs monitoring in the aquatic environment. Passive sampling offers an alternative for widespread monitoring of hydrophobic POPs in water. Most POPs have log Kow (Octanol water partition coefficient) and Log Koc (Soil Organic Carbon-Water Partitioning Coefficient) of 104 – >106 and thus preferentially partition to organic surfaces.

Passive sampling is based on the diffusion of analyte molecules from the sampled environmental medium (water) to a receiving phase in the sampling device. The diffusion occurs as a result of a difference between chemical potentials of the analyte in the two media. The net flow of analyte molecules from one medium to the other continues until equilibrium is established in the system, or until the sampling is stopped. The mass of chemical sorbed in the sampler following a given exposure period is initially proportional to the time-weighted averaged (TWA) concentration in the environmental medium to which the sampler was exposed (integrative samplers) and subsequently once equilibrium is achieved to the concentration in the environmental medium with which the device is at thermodynamic equilibrium (equilibrium samplers).

Passive samplers effectively sample large volumes of water (up to several thousand litres) when deployed for several weeks to months (Lohmann and Muir 2010) and are therefore time-integrating unlike samples collected by “active” systems. Allan et al. (2009) compared several passive devices (including LDPE, silicone and SPMDs) and liquid-liquid extraction for p,p’-DDE and PAHs, PCBs and hexachlorobenzene and concluded:

Passive samplers provide data that are less variable than that from “whole water” sampling since the latter may be strongly influenced by levels of suspended particulate matter.

Detection limits are much better with passive samplers due to high sampling rates and sampler/water partition coefficients.

30

While all passive devices performed well LDPE samplers were found to be the most reproducible.

31

Semi-permeable membrane device (SPMDs), consisting of low density polyethylene (LDPE) tubing filled with triolein, were originally developed to determine bioavailable concentrations of POPs in water (Huckins et al. 1990; Lu et al. 2002) and remain widely used for hydrophobic organics. Single-phase polymeric materials, such as LDPE strips (Adams et al. 2007), polyoxymethylene (Jonker and Koelmans 2001), and silicone (Mayer et al. 2000; Booij et al. 2002; Rusina et al. 2007) are increasingly being used.

32

33

Soil analyses are essential if POPs were used or stored on the site to analyze the pollution of soil due to POPs. Samples should be collected in accordance with protocols specified in project-specific field work instructions, and using similar SOPs to improve inter-comparability of results3. Samples should include field or trip blanks and, to the extent possible, duplicate samples to assess the precision of chemical analysis.

Customized datasheets should be created to increase efficiency in the field and reduce the likelihood of potential errors or omissions. The following general information should be collected on datasheets during sample collections:

o Date and time of sampling; o Station location (lat/long coordinate, datum, zone); o Initials of field crew members; o Sampling methods/gear used; o Number of samples collected (soil/sediment/tissue); o Number of specimens retained/released/dissected/archived (biota), or the number

of measurements taken; o Sample ID/number; o Volume of sample collected (soil/sediment/tissue); o Number of samples in composite (if individual samples are composited); o Handling techniques, preservation methods, sampling containers used;

All of the above information should be recorded on field datasheets, and secured at the end of each day. Replicated sample ID labels should be applied to datasheets and sample containers to ensure each sample has a unique ID and is not mislabeled. Sample ID labels should be affixed to the container and secured with clear tape to ensure they are

3 http://www.popstoolkit.com/sops/general+sampling+collection.aspx accessed 15 Nov, 2015

34

waterproof. The team leader must ensure that samples are collected and stored/shipped as per conditions specified by the analytical laboratory

35

Sampling gear and equipment used for field programs must be assembled and checked prior to mobilizing for the field. Equipment should be regularly inspected, maintained, and if necessary calibrated according to manufacturer’s specifics throughout the field program.

Typical equipment and materials used during field surveys are described below:

o Soil and sediment survey equipment: sediment corer and/or grab and stainless steel mixing and handling trays/utensils;

o Fish survey equipment: gill nets, seine nets, DNA sample kits, dissecting equipment, measuring board, and weight scales;

o General electronic equipment: Global Positioning System (GPS; Garmin 76, 45, 45XL, 12XL or GPSII) for obtaining sampling station positions (accuracy of ±15 m), film or digital cameras, and laptop computers with office and communication software;

o Vehicles for transportation: to be rented locally with proof of required insurance; o Safety gear and equipment: first aid kit, gloves, safety glasses, hard hat,

mosquito repellant etc.; o Reference materials: topographic maps, hydrographic charts, satellite and /or

aerial photos of study sites, publications, and previous reports; and

Miscellaneous field equipment: tarps, coolers, buckets, jerry cans, hoses, sample bottles, packing materials, assorted chemicals, waterproof pens and paper and power inverter.

36

Individual grab soil samples should be collected at locations throughout the hot spot site. If possible, these should be randomly selected and equally spaced. However, the presence of notable differences in physical soil qualities (such as staining) may necessitate the preferential selection of a sub-set of sampling locations.

Soil samples should be collected using a stainless trowel or shovel, and be collected from the top 10 cm depth (surface soils). Samples will be deposited into a stainless steel tray and will be stirred into a homogenous mixture. Samples will then be placed into one or more 125 ml or 250 ml glass jars.

37

The steps are described in detail as following:

a. Fill in the “Location Information” box on the Field Data Formb. Thoroughly clean all sampling equipment (dredge, mixing tray, spoon, etc.) with

metals-free soap and de-ionized water prior to sampling at each site. Where analyses require, use chemical solvents such as hexane and acetone to ensure all residues are dissolved from equipment surfaces.

c. Soil samples should be collected using a stainless steel core sampler, trowel or shovel.

d. Collect five sub-samples between 1 and 20cm below surface from area 1m x 1m.e. Samples are collected in a stainless steel tray and stirred into a homogenous

mixture.f. Samples are then placed into one or more separate glass jars.g. Ensure the waterproof label on the container includes the sampling site number,

date of sampling, type of sample (soil), and name of project. Also ensure that the label is securely fastened to the jar.

h. Complete a final check to ensure that the data sheet has been completed and that all required samples have been collected and are properly labeled.

i. Immediately place collected sediment samples in a cold, dark cooler.j. Ensure that the field data sheet has been completed, including photos, site map

sketch and GPS readings

If the site has been proven to be contaminated and an investigation is authorized then larger sample numbers provide more precise and reliable estimates of mean concentrations and variance. For blood and milk samples it is recommended that 50 samples are taken. For environmental variables and surveys more than 30 samples should be collected to ensure the results are statistically rigorous. The number of samples will largely depend on the area being sampled. A larger area will require more samples than a small area. Equally as important as the number of samples is the location of where samples were taken (will they accurately reflect the extent of contamination), the sampling methodologies and the QA/QC.

38

39

40

The SOP also includes the requirements for transport and storage. More specifically, these are:

Transport and storage conditions for each sample matrix including adequate facilities and infrastructure to be provided present, e.g., freezers;

Preservation of integrity of samples during transport (temperature, light, etc.); Provisions for adequate storage. These conditions are dependent on the analyte and

the matrix, but in general, the following conditions and times are proposed:− Water: Refrigerator at +4 °C− Biota and solids: Refrigerator at – 20 °C; possibly at -80 ºC when considered necessary.

Adequate storage also includes:− Registry of the performance of refrigerators and freezers, e.g., registration and control of temperature;− Availability of automatic power-supply equipment in case of power cuts;− Recommended storage times are: ∼ 2 weeks in the case of extraction,

40 days for the analysis, andseveral years for archiving samples.

Preservation of individual samples for their re-analysis (counter-sample); Pre-analytical treatment of the sample: statistical criteria to obtain sub-samples and

composite samples (pools) that are representative, homogenization of solids and tissue;

Note: there may be requirements for shipment to be addressed and respected. Especially in the case of international shipment, considerations for transport and customs’ clearance must be taken into account since restrictions may exist.

41

42

Maintenance of equipment

The maintenance of the analytical equipment is considered as one of the most important aspects in POPs analysis. It is very expensive to have service contracts for all the maintenance and therefore it is important to train the laboratory personnel to do the basic maintenance when the QA/QC results are unacceptable.

Laboratories must arrange for proper training, including basic maintenance, when new equipment is installed in the laboratories.

Training of laboratory staff

Human resources are crucial for any analytical work. The following specific problems need to be addressed and resolved:

a. The lack of skilled laboratory personnel to conduct the analytical work has been identified as one of the critical problems;b. The training requirements. Two levels of training exist:

Training of people to follow the analytical procedures and to report the results; Training of people to do troubleshooting and conduct the necessary maintenance

when the QA/QC criteria fail;c. There is a need in the region for training courses and annual training workshops for the transfer of technology know-how.

43

Housing

For POPs analytical laboratories there are certain requirements as to housing. These include:

Proper environmental conditions (humidity is a most critical factor) for instrumental analysis but also for sample preparation;

Minimization of vibration (most important for HRMS instruments); Temperature control for helium carrier gas used with ECD; At certain locations where the incoming air has to be cleaned. Ideally this would

involve a well-ventilated lab with air pre-filtered through High Efficiency Particulate Air and carbon filters. The analysis of blank samples will disclose background interferences, and to identify the influence from the laboratory environment, a small volume of a solvent left in an open Petri dish for a couple of days will catch the compounds in the atmosphere;

Occupational Health Safety venting; Environmentally sound/safe disposal of laboratory wastes and highly contaminated

samples must be guaranteed.

44

Testing of the Persistent Organic Pollutants – pesticides can be performed for two important features that form the basis of final strategy of scientific conclusion and handling:

a. Identification of the type of persistent organic pollutant in a sample at a stockpileb. Identification of pollution level/concentration of any persistent organic pollutant in

environmental and human matrices

The identification of POPs at a stockpile for the type and quality of POPs can be performed using three different techniques as following:

1. High Resolution Gas Chromatography:2. The Mass Spectrometry3. Negative Chemical Ionization Mass Spectrometry

45

Gas chromatography (GC) is a common type of chromatography used in analytical chemistry for separating and analyzing compounds that can be vaporized without decomposition. Typical uses of GC include testing the purity of a particular substance, or separating the different components of a mixture (the relative amounts of such components can also be determined). In some situations, GC may help in identifying a compound. In preparative chromatography, GC can be used to prepare pure compounds from a mixture (Pavia et. Al., 2006).

Gas chromatography is also sometimes known as vapor-phase chromatography (VPC), or gas–liquid partition chromatography (GLPC). These alternative names, as well as their respective abbreviations, are frequently used in scientific literature. Strictly speaking, GLPC is the most correct terminology, and is thus preferred by many author.

46

In gas chromatography, the mobile phase (or "moving phase") is a carrier gas, usually an inert gas such as helium or an unreactive gas such as nitrogen. The stationary phase is a microscopic layer of liquid or polymer on an inert solid support, inside a piece of glass or metal tubing called a column (an homage to the fractionating column used in distillation). The instrument used to perform gas chromatography is called a gas chromatograph (or "aerograph", "gas separator").

The gaseous compounds being analyzed interact with the walls of the column, which is coated with a stationary phase. This causes each compound to elute at a different time, known as the retention time of the compound. The comparison of retention times is what gives GC its analytical usefulness.

47

In order to measure the characteristics of individual molecules, a mass spectrometer converts them to ions so that they can be moved about and manipulated by external electric and magnetic fields. The three essential functions of a mass spectrometer, and the associated components, are:

A small sample is ionized, usually to cations by loss of an electron-the Ion Source The ions are sorted and separated according to their mass and charge-the Mass Analyzer The separated ions are then measured, and the results displayed on a chart-the Detector

Because ions are very reactive and short-lived, their formation and manipulation must be conducted in a vacuum. Atmospheric pressure is around 760 torr (mm of mercury). The pressure under which ions may be handled is roughly 10-5 to 10-8 torr (less than a billionth of an atmosphere). Each of the three tasks listed above may be accomplished in different ways. In one common procedure, ionization is effected by a high energy beam of electrons, and ion separation is achieved by accelerating and focusing the ions in a beam, which is then bent by an external magnetic field. The ions are then detected electronically and the resulting information is stored and analyzed in a computer.

48

The heart of the spectrometer is the ion source. Here molecules of the sample are bombarded by electrons issuing from a heated filament. This is called an electron-impact source. Gases and volatile liquid samples are allowed to leak into the ion source from a reservoir. Non-volatile solids and liquids may be introduced directly. Cations formed by the electron bombardment are pushed away by a charged repeller plate (anions are attracted to it), and accelerated toward other electrodes, having slits through which the ions pass as a beam. Some of these ions fragment into smaller cations and neutral fragments. A perpendicular magnetic field deflects the ion beam in an arc whose radius is inversely proportional to the mass of each ion. Lighter ions are deflected more than heavier ions. By varying the strength of the magnetic field, ions of different mass can be focused progressively on a detector fixed at the end of a curved tube (also under a high vacuum).

49

In assigning mass values to atoms and molecules, assume integral values for isotopic masses. However, accurate measurements show that this is not strictly true. Because the strong nuclear forces that bind the components of an atomic nucleus together vary, the actual mass of a given isotope deviates from its nominal integer by a small but characteristic amount (remember E = mc2 )4. Thus, relative to 12C at 12.0000, the isotopic mass of 16O is 15.9949 amu (not 16) and 14N is 14.0031 amu (not 14).

Table 2: Deviation in actual mass isotope from its normal integer

Formula C6H12 C5H8O C4H8N2

Mass 84.0939

84.0575

84.0688

When a molecule is subject to ionization by electronic impact in a mass spectrometer, the primary process consists of the abstraction of an electron to give a cation-radical.

This cation-radical treatment of the molecular ion will have main or lower trend to fragment according to its stability. Very stable molecular ions will have little trend to fragment and will be very abundant. The most frequent ion of the spectrum is called basic beak. The most

4 https://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/MassSpec/masspec1.htm. Accessed 12 Nov, 2015

50

abundant fragments of a mass spectrum give us a very valuable information on the structure of the molecule.

The interpretation of a mass spectrum is performed by applying the following rule: “A molecule will fragment in a mass spectrometer in such a way that it will form the most stable ions”

51

Chemical ionization (CI) is an ionization technique used in mass spectrometry (Munson, 1966) (Fales et. Al., 1972). Chemical ionization is a lower energy process than electron ionization (EI). The lower energy yields less or sometimes no fragmentation, and usually a simpler spectrum. The lack of fragmentation limits the amount of structural information that can be determined about the ionated species. However, a typical CI spectra has an easily identifiable protonated molecular ion peak [M+1]+ which allows for determination of molecular mass (De Hoffmann, 2003). CI is thus useful in cases where the energy from the bombarding electrons in EI is so great that impact almost exclusively causes fragmentation to occur and molecular ions are not formed in large enough quantities to produce an identifiable molecular ion peak.

Classes of molecules that have intrinsically high Negative Chemical Ionization (NCI) sensitivities are molecules that are oxidizing agents, alkylating agents, or both. These classes of molecules span a large portion of the spectrum of the toxic substances that appear in the environment and, as a result, one of the major applications of NCIMS has been in the detection and analysis of toxic substances (Dougherty, 1981). Chemical ionization for gas phase analysis is either positive or negative.

52

In a CI experiment, ions are produced through the collision of the analyte with ions of a reagent gas that are present in the ion source. Some common reagent gases include: methane, ammonia, and isobutane. Inside the ion source, the reagent gas is present in large excess compared to the analyte. Electrons entering the source will preferentially ionize the reagent gas. The resultant collisions with other reagent gas molecules will create an ionization plasma. Positive and negative ions of the analyte are formed by reactions with this plasma.

53

54

55

In most aspects, POPs analysis does not differ from any other chemical analysis for determination of the mass concentration of an analyte of interest in a given matrix. Therefore, this guidance includes elements of common sense practices such as aspects of the “Principles of Good Laboratory Practice” (OECD 1998) and descriptions found elsewhere or already being in place at laboratories because of other types of chemical analysis. Nevertheless, there are certain criteria specific for POPs analysis and these should be taken into consideration when performing analysis to serve the environmental multilateral agreements such as the Stockholm, Rotterdam or Basel Conventions.

As for any other chemical analysis, POPs analysis includes the following three main steps:

a) Sampling;b) Transport and storage of the samples;c) Analysis (extraction, purification, separation, identification, quantification and

reporting).

Laboratories may adopt EU / EPA / AOAC / ASTM, etc., methods or other published methods for sample extraction, clean up, and analysis, and have to validate them within the laboratory.

56

General laboratory environmental conditions should ensure enough laboratory space for each step of the analysis and to avoid interference between individual samples. This includes:

Physical separation of standards and samples according to their origin (for example, industrial versus environmental) or

Expected POP concentration (minimize cross-contamination by separating highly contaminated samples from low contaminated samples)

Control of temperature and provision of air-conditioning; Availability of extraction hoods; Handling area of inflammable products; Provisions for laboratory waste disposal

Ensure the custody chain of the sample: verify the integrity and preservation of the samples (maintenance) in terms of temperature, containers, labels, registry, those responsible at each stage, establishment of acceptance criteria (conditions as well as quantity of material, according to analyte and matrix);

Separation of aliquots: In the case of complementary analysis (for example, granulometry) prior to the freezing of the sample;

Selection and validation of analysis method: Use method validation protocol according to the type of analyte and matrix (selectivity, repeatability, ability to reproduce, extraction efficiency, recovery, detection limit, quantification limit, accuracy). Quality of solvents and reagents (blanks). Clean glass material (avoid cross-contamination). Maintenance and calibration of auxiliary equipment (stoves, scales, test tubes, pipettes, glassware). Protocols and procedures must be clearly described and documented.

57

There are various methods for extraction, which include Soxhlet, SFE, PFE, liquid-liquid, etc. After extraction, the extract will be concentrated. In order to do so, the technique should be optimized to avoid excessive loss of the analyte. Typically, this step includes: evaporation under vacuum or with nitrogen (Note: control of temperature, flow of nitrogen, and vacuum are essential). Complete drying of the extract should be avoided.

Before or during extraction, water, lipids, proteins, and sulfur should be eliminated. This can be done by: Elimination of water by drying of the sample with sodium sulphate or

equivalent demonstrated acceptable drying procedure Elimination of lipids with sulfuric acid or permeation in gels after extraction Denaturation of proteins with oxalate Elimination of sulfur with activated copper or by gel permeation after

extraction. Extraction should be standardized with respect to standardization of extraction

times, type of solvent, performance of auxiliary equipment, etc.; Before extraction, internal standards should be added to control the extraction

efficiency; The recoveries of the extraction standards differ with POP to be analyzed and

matrix.

Based on current experiences (from international calibration studies) as a general rule:

For PCB and pesticides: 80 %-120 % (for tetra- and penta-chlorinated PCB, recoveries down to 60 % can be accepted)

For PCDD/PCDF: 50 %-130 % (for hepta- and octa-chlorinated PCDD/PCDF 40 %-150 % can be accepted)

58

Purification is done to remove interfering substances/materials from the analyte in order to obtain unambiguous results. Purification should be efficient enough so that the chromatographic retention is not influenced by the matrix (especially when no labelled internal standards are used or no mass-specific detection is present).

Purification is being performed with various types of adsorbents with different solvents depending on selectivity, conditioning, and column flow. During purification the following aspects need to be controlled or maintained:

Verification that profile/pattern (relative amounts within the sample) of the analytes is maintained throughout the whole purification procedure. In other words that at a satisfying recovery the pattern/profile of the analytes at the original composition are obtained;

An internal standard is added at a concentration signal/noise at a minimum level with at least 20/1; with fixed concentrations of internal standards from sample to sample in order to obtain adequate response factors;

Control fraction cut.

59

Separation of POPs will be conducted through gas chromatography with electronic capture detector (ECD), mass selective detector or, if available, high-resolution mass spectrometry (HRMS). Presently, only high-resolution gas chromatography (= capillary gas chromatography) can achieve sufficient separation. Packed columns (GC) or other separation techniques such as HPLC were not found adequate.

In general, an appropriate GC phase has to be selected and enough GC peak separation must be achieved to allow accurate quantification (general numeric criteria cannot be given, but the use of capillary columns with lengths of 30-60 m, internal diameters of 0.15-0.25 mm, a film thickness of 0.1-0.3 μm, and helium or hydrogen as a carrier gas should ensure sufficient resolution) (note: hydrogen cannot be used together with MS detection);

Separation of critical isomer pairs and congeners has to be verified, e.g., pairs of PCB 28 and 31, 118 and 149, etc.; in dioxin analysis separation of PCDD/PCDF from polychlorinated diphenyl ethers (PCDE) should be checked;

60

For ECD (or more general, for non-MS detectors), confirmation of peaks should be performed on a second column with different polarity;

For MS detection, confirmation of peaks on a second column with different polarity can be advisable;

For PCB analysis and ECD detection, a minimum of two internal standards - one eluting at the beginning and one at the end of the chromatogram – should be used. It is recommended to also use one PCB congeners that elutes in the middle of the chromatogram. Thus, the following three congeners are recommended: PCB #112, #155, and #198. These three congeners are quite stable and typically not found in commercial PCB mixtures. Note: decachlorobiphenyl (PCB #209) is not recommended because it tends to precipitate easily in standard solutions and due to long retention times, the peaks tend to be broad and have tailings. PCB #209 has also be identified in environmental samples and could not be quantified if this congener is selected as an internal standard.

Adequate handling and preservation of all standards and reference materials; Verification of chromatographic conditions include:

Resolution, symmetric peak shape Reproducibility of retention times Purity of gases Use of second column of different polarity as confirmation column Verification of the linear range of the instrument.

61

Standard solutions should be prepared and stored on w/w basis rather than w/v; Multi-level calibration curves of at least 5 points; Periodical calibration (for example 1-2 times a week) and verification with daily

intermediate level standard (define a rejection criterion of, for example, ±10 %). Calibration of the detector: The instrumental MS detector detection limits needed

are a few (1-3) pg·μl-1; for HRMS the instrument detection limit is 0.1-3 pg μl-1 ; The signal to noise ratio must be equal or higher than 3:1;

62

Ensure cleanliness and superficial inertia of injector (deactivated glass insert, evaluate activity with an acceptance criterion, for example, for DDE/DDT < 20 %)

Verify the split/splitless relation, flows and state of septum Repeatability must be ensured (for example, criterion < 5 %), and Injection sequence for each group of samples analyzed as: blanks, control

samples, duplicates, verification standards Registration and traceability of services and performance of equipment

63

Retention time should match between sample and internal standard; Identification criteria include:

Positive identification should be done on isotopic ratios within 20 % of theoretical value;

For positive identification with MS detection, the retention time of the labeled internal standard to the native compound should be within 3 seconds;

Retention time ± 0.2 min for ECD or a specified percentage of the retention time of the labelled internal standard for MS detectors;

Matrix spikes (or co-injection) are recommended to verify components and check the quantification;

Integration: select the basic level and the adequate signal to noise relation of integration according to the type of sample, verify the general form of the chromatogram, the form of the peaks and manually verify integration.

The use of MS libraries is useful (if full scan); For HRGC-ECD combinations, the following specific recommendations are given:

Deactivated inlet liner in injectors has to be used; Criteria for the type and purity of carrier gas for the column. Helium is a better

choice to achieve the desired separation of pesticide POPs and PCB. The best carrier gas to achieve the required separation is hydrogen but it has

some safety risk. If all the precautions & safety procedures are in place a hydrogen generator may be considered;

Criteria for the purity of nitrogen as detector make-up gas; Sample clean-up procedures must be efficient to prevent contamination of

ECD. For HRGC-MS detection combinations, the following specific recommendations are

given: Helium as carrier gas (the only choice); Deactivated inlet liner in injectors has to be used; Vacuum conditions of instrument; Mass calibration and tuning of instrument;

64

Positive identification criteria: isotopic ratio should be within 15 % of theoretical value.

65

Quantification of the analyte should be done according to the internal standard methodology. For PCDD/PCDF and dioxin-like PCB, typically additional requirements are needed. The following requirements are considered to be indispensable:

For preparation and maintenance of standard solutions and especially under not stable laboratory atmospheric conditions, it is recommended to use w/w basis rather than w/v (weight-to-weight rather than weight-to-volume);

At least one standard representative for the POPs analyte group analyzed should be added at the normal level of quantification;

For quantification it must be assured that the concentration of the compounds/analytes is within the previously determined linear range of the detector (Note: Not necessary when multi-level calibration is performed!);

Verification that the concentration of blanks is significantly lower than the samples; recommendation: < 10-times; and

Noise should be defined as close as possible to the peak of interest; The stipulated reporting concentration has been reached; For mass spectrometry (MS detectors), at least 10 data-points should be sampled

across a mass peak for quantification (Note: Some instruments do so automatically);

The performance for each sample to be achieved should be: LOD for PCDD/PCDF of at least 1/5 LOQ of 1/5 for all other POPs of the regulatory value to be controlled/to get

meaningful results; Criteria should be set to define lower-bound and upper-bound concentrations; The reporting value and therefore the limit of quantification should be at least 1/5

of the regulatory limit or level of interest or baseline;

66

Data compilation and reporting together with data storage are the final steps in analysis. The report form must include:

Reporting should be done in accordance to regulation(s); The report has to include date, name of the sample and description (sampling,

etc.), method used, the name of staff that has performed analysis, and signature of person in charge of the POPs laboratory;

Only SI units (International System) should be used and should be verified before clearing the report;

Clear references to the material must be given, e.g., fresh weight, dry matter, lipid based;

Data should be reported as "<LOQ value" or other bound as per regulatory requirements (and not as ND);

Recovery efficiency should be reported; Uncertainty: Information on uncertainty should be made available; The reporting value should be at least 1/5 of the regulatory limit or level of

interest or baseline concentration (also covered under Quantification); The difference between lower-bound and upper-bound value at the regulatory

level should be less than 20 %; Reported values should not be corrected for percentage of recovery since the

internal standard methods does so automatically; Criteria should be built in to guarantee that sensitivity/recovery issues do not

impact the reporting values. Enough assurance should be given that the used reporting limits are fully guaranteed;

It should be demonstrated that the blank is 10-times lower than the value that is reported.

Reporting values should not be corrected by laboratory blanks (Note: There may be high fluctuations for laboratories' blanks, e.g., for PCB 118). Handling of all blanks needs written documentation; in the case of high laboratory blanks; handling of such cases and justification should be clearly indicated in the SOP;

67

68

69

70

71

72

73

74

During work with POPs whether analytical or disposal, the equipment used could be contaminated with POPs. Therefore, care is necessary for handling and disposal of equipment contaminated with POPs. Following key points should be considered while handling the contaminated equipment:

a. The workers/handlers should be provided the proper personal protective equipment b. Contaminated equipment should be identified, labeled and geo-reference to follow up on

their location and existence.c. Label equipment with POPs that contaminated the equipmentd. Isolate the contaminated equipment for proper and final disposale. In addition to isolating the equipment apply a tape indicating the hazardf. Use a drip tray or absorbent material in case of leakage g. If leakage take out of service immediately h. Check equipment periodically for leakagei. Inform personnel about danger and measures in case of accidents. j. Disposal of equipment and POPs should be reflected in the reduction of inventory.

75

Develop a waste disposal plan specific to the POPs concerned. Types of wastes in this case include the following which should be disposed-off as contaminated materials: Used kits Sawdust Absorbent materials Tools Gloves Rags.

Training of staff and operators on regular basis with pre-decided frequency. The training topics should include best practices on pollution prevention and reduction.

There should be adequate security and control measures at the POPs sites The workers/handlers should be provided the proper personal protective equipment

76

Cross-contamination of chemicals is the unintentional transfer of chemical contaminants (including POPs) from one object or equipment to another or to the person. Food, equipment, contact surfaces and people are considered important sources of cross-contamination.

POPs residues on equipment and sampling tools and contact surfaces may provide opportunities for cross contamination. For example contamination of sampling and handling equipment with POPs due to inappropriate washing and sanitation of equipment and materials including the PPEs and clothing.

The workers also contribute to the cross contamination when they do not follow the best practices of handling the equipment contaminated with POPs.

Cross-contamination is usually preventable. To decrease the chances of cross-contamination following guidelines may be followed:

a. Make sure that POPs and equipment are properly labeledb. Do not stack the equipment and glassware containing POPsc. Minimize cross-contamination by separating highly contaminated objects from low

contaminated or pollution free objectsd. Not placing equipment (containers or boxes) that may have been stored on the

floor where POPs are also stored onto other contact surfacee. Cleaning and sanitizing equipment between usesf. Using correct sanitation procedures for all equipment and clothingg. Keep contaminated equipment away from children, food items and animalsh. Flow of operations at the POPs site should minimize the likelihood of cross

contamination i.e. the area should be isolated and better fencedi. Color coded clean equipment should be used for each type of POPsj. Training of workers is necessary so that workers should be able to identify a

potential cross contamination situation and prevent it from happening

77

k. Protecting technicians against POPs exposure by protective clothing including overalls, boots or overshoes, gloves, and eye protection

l. For preventing leakages and spills during the transportation of POPs, loading areas are recommended to have adequate spill prevention and control as well as clean-up materials

m. Gloves are used to protect skin from chemicals and infectious materials.  Once used, gloves are considered contaminated.  Gloves must be removed upon exiting the contaminated area or the lab to prevent cross contamination of commonly used surfaces.  As a general rule, never touch elevator buttons, door handles, etc. while wearing gloves

n. Once gloves are removed, they must be placed into Stericycle box or hazard waste container.  Gloves should not be placed in regular trash

o. Transport POPs and samples safely.  If carrying POPs from one location to another remember to use a sealed container with lid and a secondary container with a secure lid to transport the POPs.  Place an extra pair of clean gloves in your pocket

p. Make sure workstations, equipment, and utensils are cleaned and sanitized

78

Labeling of products and articles consisting of, containing or contaminated with POPs is critical for the success of inventories and is a basic safety feature of any waste management system. Each waste container should be labeled to identify the container (e.g., ID number), the POPs present and the hazard level. Labeling of POP contaminated materials and containers is a basic safety feature and important for the success of any waste management system.

The first place to look for information is the label which should be securely fixed to the contaminated material container. The label should include the following information:

a. A recommended hazard colour codeb. A POPs Identification number will be very helpfulc. Product or brand name d. Details including location of POPs with GPS coordinatese. Safety precautions f. First aid advice in case of poisoningg. Hazards and precautions including protective equipment adviceh. Storage information

The label should be in a locally understood language and printed clearly enough to be easily readable. The labels should also be regularly inspected to ensure that labels are present and readable. Containers without labels or with unreadable labels should be considered obsolete and taken out of use.

79

Usually the POPs contaminated materials are required to be stored temporarily at a location before final disposal. Final disposal needs careful implementation of certain activities therefore, temporary storage is necessary. Storing POPs contaminated materials in inappropriate conditions could lead to the contamination of adjacent soils such as agricultural fields and water bodies.

Even for temporary purpose a proper site should be provided or engaged for storing materials contaminated with POPs. It could be a laboratory facility or at the site where POPs are stored. Nevertheless, following conditions should be kept in mind while temporarily storing the POPs contaminated equipment and materials:

a. The conditions of the temporary storage site (walls, floor, ceiling, ventilation, drainage, etc.) as well as the safety measures to be used in case of an accident of some type must be fully considered so as to minimize risks.

b. Store equipment and materials well packed in plastic bags tightly closed.c. Proper labeling should be done for each piece of the stored equipment.d. Within a storage facility and at storage areas that form part of the site, signs should

indicate the materials that are stored, with warnings, and any general housekeeping practices that should be followed in the storage area (e.g., segregation).

e. Leak detection and secondary containment should be considered if release presents a risk to a water body or groundwater.

f. The storage area should have an impermeable, hard-standing floor with good drainage; it should be easy to clean and disinfect.

g. The storage area should afford easy access for staff in charge of handling the stored materials.

h. It should be possible to lock the store to prevent access by unauthorized persons.i. Easy access for collection vehicles is essential.j. The storage area should be inaccessible for animals, insects, and birds.k. There should be good lighting and at least passive ventilation.

80

l. A supply of cleaning equipment, protective clothing, and waste bags or containers should be located conveniently close to the storage area.

81

Transportation of materials contaminated with POPs is as important as POPs themselves. It is important to avoid accidental spills during transportation and to track POPs contaminated materials until it reaches its ultimate destination.

POPs contaminated materials are a type of waste that should be properly packaged for ease of transport and as a safety measure to reduce the risk of leaks and spills. Packaging of hazardous wastes falls into two categories: packaging for transport and packaging for storage.

POPs contaminated materials should be transported in an environmentally sound manner to avoid accidental spills and to track their transport and ultimate destination appropriately. Before transport, contingency plans should be prepared in order to minimize environmental impacts associated with spills, fires and other emergencies that could occur during transport.

During transportation, such wastes should be identified, packaged and transported in accordance with the “United Nations Recommendations on the Transport of Dangerous Goods: Model Regulations (Orange Book)”.

Persons transporting such wastes should be qualified and certified as carriers of hazardous materials and wastes. Companies transporting POPs contaminated materials and wastes within the country should be certified as carriers of hazardous materials and wastes, and their personnel should be qualified.

82

83

The main concerns when handling POPs wastes are human exposure, accidental release to the environment and contamination of other waste streams with POPs. Such wastes should be handled separately from other waste types in order to prevent contamination of other waste streams. Recommended practices for this purpose include:

(a) Inspecting containers for leaks, holes, rust or high temperature, and appropriate repackaging and relabeling as necessary;

(b) Handling wastes at temperatures below 25°C, if possible, because of the increased volatility at higher temperatures;

(c) Ensuring that spill containment measures are adequate and would contain liquid wastes if spilled;

(d) Placing plastic sheeting or absorbent mats under containers before opening them if the surface of the containment area is not coated with a smooth surface material (paint, urethane or epoxy);

(e) Removing liquid wastes either by removing the drain plug or by pumping with a peristaltic pump and suitable chemical-resistant tubing;

(f) Using dedicated pumps, tubing and drums, not used for any other purpose, to transfer liquid wastes;

(g) Cleaning up any spills with cloths, paper towels or absorbent;(h) Triple rinsing of contaminated surfaces with a solvent;(i) Treating all absorbents and solvent from triple rinsing, disposable protective

clothing and plastic sheeting as wastes containing or contaminated with POPs when appropriate; and

(j) Staff should be trained in the correct methods of handling POPs wastes.

84

Although large industries may be responsible for the proper management of POPs wastes that they generate or own, many smaller entities also possess such wastes. The POPs wastes possessed by small entities may include household- or commercial-sized pesticide containers, PCB fluorescent light ballasts, small containers of pentachlorophenol-based wood preservatives with PCDD and PCDF contamination, small amounts of “pure” POPs in laboratories and research facilities, and pesticide-coated seeds used in agricultural and research settings. To deal with this scattered assortment of hazardous wastes, many governments have established depots where small quantities of these wastes can be deposited by the owner at no charge or for a nominal fee. These depots may be permanent or temporary in nature, or may be located at existing commercial hazardous-waste transfer stations. Waste-collection depots and transfer stations may be set up on a regional basis by groups of countries or may be provided by a developed country to a developing country.

Care should be taken in establishing and operating waste collection programmes, depots and transfer stations:

(a) To advertise the programme, depot locations and collection time periods to all potential holders of POPs wastes;

(b) To allow enough time of operation of collection programmes for the complete collection of all potential POPs wastes;5

(c) To include, to the extent practical, all POPs wastes in the programme;(d) To make acceptable containers and safe-transport materials available to waste

owners for those waste materials that may need to be repackaged or made safe for transport;

(e) To establish simple, low-cost mechanisms for collection;(f) To ensure the safety both of those delivering waste to depots and workers at the

depots;(g) To ensure that the operators of depots are using an accepted method of disposal;

5 Complete collection may require the depots to operate either continuously or intermittently over several years.

85

(h) To ensure that the programme and facilities meet all applicable legislative requirements;

(i) To ensure separation of POPs wastes from other waste streams.

86

POPs wastes should be properly packaged for ease of transport and as a safety measure to reduce the risk of leaks and spills. Packaging of hazardous wastes falls into two categories: packaging for transport and packaging for storage.

Some general precepts for packaging of POPs wastes for storage are as follows:

(a) Packaging that is acceptable for transport is, in most cases, suitable for storage;(b) Such wastes in their original product containers are generally safe for storage if

the packaging is in good condition;(c) Such wastes should never be stored in product containers that were not intended

to contain such wastes or that have labels on them that incorrectly identify the contents;

(d) Containers that are deteriorating or are deemed to be unsafe should be emptied or placed inside a sound outer package (overpack). When unsafe containers are emptied, the contents should be placed in appropriate new or refurbished containers. All new or refurbished containers should be clearly labelled as to their contents;

(e) Smaller containers can be packaged together in bulk by placing them in appropriate or approved larger containers containing absorbent material;

(f) Out-of-service equipment containing POPs may or may not constitute suitable packaging for storage. The determination of safety should be made on a case-by-case basis.

87

POPs pesticides should be disposed-off in an environment friendly manner to avoid risk to humans, plants and animals and the ecosystem. Unplanned and unsafe disposal may lead to discharges in to the environment that would cause detrimental impacts. Disposal methods for the destruction and irreversible transformation of POPs wastes in the following section have been selected according to two criteria:

a) Destruction Efficiency level achieved b) Commercial availability

PretreatmentFollowing pretreatment steps should be carried out for environmentally sound disposal of POPs wastes:

Adsorption and absorption“Sorption” is the general term for both absorption and adsorption processes. Sorption is a pre-treatment method that uses solids for removing substances from liquids or gases. Adsorption involves the separation of a substance (liquid, oil, gas) from one phase and its accumulation at the surface of another (activated carbon, zeolite, silica, etc.). Absorption is the process whereby a material transferred from one phase to another interpenetrates the second phase. For example, contaminants transferred from liquid phase onto granular activated carbon (GAC). GAC is widely applied in the removal of organic contaminants in wastes waters because of the effectiveness, versatility and relatively low-cost of this method.

Adsorption and absorption processes can be used to concentrate contaminants and separate them from aqueous wastes and from gas streams. The concentrate and the adsorbent or absorbent may require treatment prior to disposal.

Dewatering

88

Dewatering is a pre-treatment process that partially removes water from the wastes to be treated. Dewatering can be employed for disposal technologies that are not suitable for aqueous wastes. For example, water will react explosively with molten salts or sodium. Depending on the nature of the contaminant, the resulting vapours may require condensation or scrubbing, and further treatment.

Mechanical separation Mechanical separation can be used to remove larger-sized debris from the waste stream or for technologies that may not be suitable for both soils and solid wastes.

MixingMixing of materials prior to waste treatment may be appropriate in order to optimize treatment efficiencies. However, mixing of wastes with POP contents above a defined low POP content with other materials solely for the purpose of generating a mixture with a POP content below the defined low POP content is not environmentally sound.

Oil-water separationSome treatment technologies are not suitable for aqueous wastes; others are not suitable for oily wastes. Oil-water separation can be employed in these situations to separate the oily phase from the water. Both water and oily phase may be contaminated after the separation and both may require treatment.

pH adjustmentSome treatment technologies are most effective over a defined pH range and in these situations alkali, acid or CO2 are often used to control pH levels. Some technologies may also require pH adjustment as a post-treatment step.

Size reduction Some technologies are able to process wastes only within a certain size limit. For example, some may handle POP-contaminated solid wastes only if they are less than 200 mm in diameter. Size reduction can be used in these situations to reduce the waste components to a defined diameter. Other disposal technologies require slurries to be prepared prior to injection into the main reactor. It should be noted that facilities may become contaminated when reducing the size of POPs wastes. Precautions should therefore be taken to prevent subsequent contamination of POP-free waste streams.

Solvent washingSolvent washing can be used to remove POPs from electrical equipment such as capacitors and transformers. This technology has also been used for the treatment of contaminated soil and sorption materials used in adsorption or absorption pre-treatment.

Thermal desorptionLow-temperature thermal desorption, also known as low-temperature thermal volatilization, thermal stripping and soil roasting, is an ex-situ remedial technology that uses heat physically to separate volatile and semi-volatile compounds and elements (most commonly petroleum hydrocarbons) from contaminated media (most commonly excavated soils). Such processes have been used for the decontamination of the non-porous surfaces of electrical equipment such as transformer carcasses that formerly contained PCB-containing dielectric fluids. Thermal desorption of wastes containing or contaminated with POPs may result in the formation of unintentional POPs which may require additional treatment.

Membrane filtration

89

Membrane filtration is a thin film separation of two or more components in a liquid and is used as an option for conventional wastewater treatment. It is a pressure- or vacuum-driven separation process in which contaminants may be rejected by an engineered barrier, primarily through a size-exclusion mechanism. Different classifications of membrane treatment applicable to POPs include nanofiltration and reverse osmosis.

90

91

Process description: Alkali metal reduction involves the treatment of wastes with dispersed alkali metal. Alkali metals react with chlorine in halogenated waste to produce salts and non-halogenated waste. Typically, the process operates at atmospheric pressure and temperatures between 60°C and 180°C.6 Treatment can take place either in situ (e.g., PCB-contaminated transformers) or ex situ in a reaction vessel. There are several variations of this process. (Piersol, 1989). Although potassium and potassium-sodium alloy have been used, metallic sodium is the most commonly used reducing agent. The remaining information is based on experiences with the metallic sodium variation.

Efficiency: Destruction efficiency (DE) values of greater than 99.999 per cent and destruction removal efficiency (DRE) values of 99.9999 per cent have been reported for aldrin, chlordane and PCBs (Ministry of Environment of Japan, 2004). The sodium reduction process has also been demonstrated to meet regulatory criteria in Australia, Canada, Japan, South Africa, the United States of America and the European Union for PCB transformer oil treatment, i.e., less than 2 ppm in solid and liquid residues (Piersol 1989 and UNEP, 2004b).

Waste types: Sodium reduction has been demonstrated with PCB-contaminated oils containing concentrations up to 10,000 ppm. Some vendors have also claimed that this process is capable of treating whole capacitors and transformers (UNEP, 2004b).

Pre-treatment: Ex-situ treatment of PCBs can be performed, however, following solvent extraction of PCBs. Treatment of whole capacitors and transformers could be carried out following size reduction through shearing. Pre-treatment should include dewatering by phase separation, evaporation, or other method (UNIDO, 1987) to avoid explosive reactions with metallic sodium. “PCB oils may need to be extracted from equipment and the latter washed with organic solvents. Similarly the POPs

6 Ariizumi Otsuka, Kamiyama and Hosomi, 1997; and Japan Industrial Waste Management Foundation, 1999.

92

which are solid or in the adsorbed state would need to be dissolved to the required concentration or extracted from matrices (Piersol 1989 and UNEP, 2004b).

Emissions and residues: Air emissions include nitrogen and hydrogen gas. Emissions of organic compounds are expected to be relatively minor (Piersol, 1980). It has been noted, however, that PCDDs and PCDFs can be formed from chlorophenols under alkaline conditions at temperatures as low as 150°C (Weber, 2004). Residues produced during the process include sodium chloride, sodium hydroxide, polyphenyls and water. In some variations, a solidified polymer is also formed (UNEP, 2000b).

Release control and post-treatment: After the reaction, the by-products can be separated out from the oil through a combination of filtration and centrifugation. The decontaminated oil can be reused, the sodium chloride can either be reused or disposed of in a landfill and the solidified polymer can be disposed of in a landfill (UNEP, 2000b). “No or minimal post-treatment is required. Depending on technology such can include off-gas treatment and neutralization or conservation of residuals. The excess of sodium, if not neutralized, may need to be recovered. Liquid products, if not reused, and solidified polymeric products should be usually burnt in incinerators and inorganic salts would require disposal. Minor quantities of volatile organics in emissions can be captured by activated carbon.” (UNIDO, 2007)

Energy requirements: Immediate energy requirements are expected to be relatively low owing to the low operating temperatures associated with the sodium reduction process.

Material requirements: Significant amounts of sodium are required to operate this process (UNEP, 2004b).

Portability: The process is available in transportable and fixed configurations (UNEP, 2000b)

Health and safety: Dispersed metallic sodium can react violently and explosively with water, presenting a major hazard to operators. Metallic sodium can also react with a variety of other substances to produce hydrogen, a flammable gas that is explosive in admixture with air. Great care must be taken in process design and operation absolutely to exclude water (and certain other substances, e.g., alcohols) from the waste and from any other contact with the sodium.

Capacity: Mobile facilities are capable of treating 15,000 litres per day of transformer oil (UNEP, 2000b).

Other practical issues: Sodium reduction used for in-situ treatment of PCB-contaminated transformer oils may not destroy all the PCBs contained in the porous internals of the transformer. Some authors have noted that there is a lack of information on the characterization of residues (UNEP, 2000b).

93

Process description: The BCD process involves treatment of wastes in the presence of a reagent mixture consisting of hydrogen-donor oil, alkali metal hydroxide and a proprietary catalyst. When the mixture is heated to above 300°C, the reagent produces highly reactive atomic hydrogen. The atomic hydrogen reacts with the waste to remove constituents that confer the toxicity to compounds.

Efficiency: DEs of 99.99–99.9999 per cent have been reported for DDT, PCBs, PCDDs and PCDFs (UNEP, 2000b). DEs of greater than 99.999 per cent and DREs of greater than 99.9999 per cent have also been reported for chlordane (Ministry of the Environment of Japan, 2004). It has also been reported that reduction of chlorinated organics to less than 2 mg/kg is achievable (UNEP, 2001).

Waste types: BCD should be applicable to other POPs in addition to the waste types listed above (UNEP, 2004b and Vijgen 2002). BCD should be capable of treating wastes with a high POP concentration, with demonstrated applicability to wastes with a PCB content of above 30 per cent Vijgen, 2002). It was believed that in practice, the formation of salt within the treated mixture could limit the concentration of halogenated material able to be treated. However, the vendor has indicated that the build-up of salt within the reactor simply limits the amount of waste that can be fed to the reactor and that this problem does not appear unsolvable. Applicable waste matrices include soil, sediment, sludge and liquids. The company BCD Group also claims that the process has been shown to destroy PCBs in wood, paper and metal surfaces of transformers.

Pre-treatment: Soils may be treated directly. Different types of soil pre-treatment may be necessary:

(a) Larger particles may need to be removed by sifting and crushed to reduce their size; or

(b) pH and moisture content may need to be adjusted.

94

Emissions and residues: Air emissions are expected to be relatively minor. The potential to form PCDDs and PCDFs during the BCD process is relatively low. However, it has been noted that PCDDs can be formed from chlorophenols under alkaline conditions at temperatures as low as 150°C (Weber, 2004). Other residues produced during the BCD reaction include sludge containing primarily water, salt, unused hydrogen-donor oil and carbon residue. The vendor claims that the carbon residue is inert and non-toxic. For further details, users are referred to the literature produced by BCD Group, Inc.

Energy requirements: Energy requirements are expected to be relatively low owing to the low operating temperatures associated with the BCD process.

Material requirements:

(a) Hydrogen-donor oil, such as No. 6 fuel oil or Sun Par oils No. LW-104, LW-106 and LW-110;

(b) Alkali or alkaline earth metal carbonate, bicarbonate or hydroxide, such as sodium bicarbonate. The amount of alkali required is dependent on the concentration of the halogenated contaminant contained in the medium. Amounts range from 1 per cent to about 20 per cent by weight of the contaminated medium; and

(c) Proprietary catalyst amounting to 1 per cent by volume of the hydrogen donor oil.

The equipment associated with this process is thought to be readily available (Rahuman et al, 2000).

Portability: Modular, transportable and fixed plants have been built.

Health and safety: In general, the health and safety risks associated with operation of this technology are thought to be low, although a BCD plant in Melbourne, Australia, was rendered inoperable following a fire in 1995. The fire is thought to have resulted from the operation of a storage vessel without a nitrogen blanket. Some associated pre-treatments such as alkaline pre-treatment of capacitors and solvent extraction have significant fire and explosion risks, although they can be minimized through the application of appropriate precautions.

Capacity: BCD can process as much as 2,500 gallons per batch, with a capability of treating two–four batches per day (Vijgen, 2002).

State of commercialization: BCD has been used at two commercial operations within Australia, with one still operating. Another commercial system has been operating in Mexico since 1999. In addition, BCD systems have been used for short-term projects in Australia, Spain and the United States of America. A BCD unit for the treatment of both soil and pesticide wastes contaminated with PCDDs and PCDFs is now in operation within the Czech Republic.

95

Process description: CHD involves the treatment of wastes with hydrogen gas and palladium on carbon (Pd/C) catalyst dispersed in paraffin oil. Hydrogen reacts with chlorine in halogenated waste to produce hydrogen chloride (HCl) and non-halogenated waste. In the case of PCBs, biphenyl is the main product. The process operates at atmospheric pressure and temperatures between 180°C and 260°C (Sakai, Peter and Oono, 2001; Noma, Sakai and Oono, 2002; and Noma, Sakai and Oono, 2003a and 2003b).

Efficiency: DEs of 99.98–99.9999 per cent have been reported for PCBs. It has also been reported that a reduction of the PCB content to less than 0.5 mg/kg is achievable.

Waste types: CHD has been demonstrated with PCBs removed from used capacitors. PCDDs and PCDFs contained in PCBs as impurities have also been dechlorinated. A vendor has also claimed that chlorinated wastes in liquid state or dissolved in solvents can be treated by CHD.

Pre-treatment: PCBs and PCDDs/PCDFs must be extracted using solvents or isolated by vaporization. Substances with low boiling points such as water or alcohols should be removed by distillation prior to treatment.

Emission and residues: No emissions would occur during the dechlorination reaction because it takes place in the closed hydrogen circulation system. HCl is not discharged from the reaction because it is collected with water as hydrochloric acid within the circulation system. Biphenyl isolated after the reaction by distillation does not contain any toxic materials.

Release control and post-treatment: Biphenyl, the main product, is separated out from the reaction solvent by distillation after the reaction, and the catalyst and reaction solvent are reused for the next reaction.

96

Energy requirements: Energy requirements are expected to be relatively low owing to the low operating temperatures associated with the CHD process.Material requirements: The CHD process requires the same number of atoms of hydrogen as those of chlorine in the PCBs, and also 0.5 per cent by weight of catalyst.

Portability: CHD is available in fixed and transportable configurations depending on the volume of PCBs to be treated.

Health and safety: The use of hydrogen gas requires adequate controls and safeguards to ensure that explosive air-hydrogen mixtures are not formed.

Capacity: In Japan, a plant which is capable of treating 2 Mg PCB per day using the CHD process was constructed and is in operation. HydroDec runs plants in Canton, USA and in Young, Australia. Their capacity is not mentioned.

Other practical issues: There are many reports about PCB de-chlorination by using CHD. Generally, Pd/C catalyst shows the largest degradation rate compared to the other supported metal catalysts. Reaction temperature can be increased to 260°C when paraffin oil is used as reaction solvent.

State of commercialization: In Japan, a commercial-scale plant was constructed at JESCO Osaka facility in 2006 and PCB extracted form transformers and capacitors are treated by the CHD process (JESCO, 2009).

97

Process description: Cement kilns typically consist of a long cylinder of 50–150 metres, inclined slightly from the horizontal (3 per cent to 4 per cent gradient), which is rotated at about 1-4 revolutions per minute. Raw materials such as limestone, silica, alumina and iron oxides are fed into the upper or “cold” end of the rotary kiln. The slope and rotation cause the materials to move toward the lower or “hot” end of the kiln. The kiln is fired at the lower end of the kiln, where material temperatures reach 1,400°C–1,500°C. As the materials move through the kiln, they undergo drying and pyroprocessing reactions to form clinker.

Efficiency: DREs of greater than 99.99998 per cent have been reported for PCBs in several countries (Ahling, 1979; Benestad, 1989; Lauber, 1987; Mantus, 1992. US-EPA, 1986; Lauber, 1982; von Krogbeumker, 1994; Black, 1983). A facility should demonstrate its capability to destroy (combustion) or remove (settling in ductwork or air pollution control devices) at least 99.9999 % of targeted POPs.

Waste types: As mentioned above, cement kilns have been demonstrated with PCBs, but should be applicable to other POPs. Cement kilns are capable of treating both liquid and solid wastes.

Pre-treatment: Pre-treatment can involve:

(a) Thermal desorption of solid wastes;(b) Homogenization of solid and liquid wastes through drying, shredding, mixing and

grinding. (c) Size reduction

Emissions and residues: Emissions may include, inter alia, nitrogen oxides, carbon monoxide, sulphur dioxide and other oxides of sulphur, metals and their compounds, hydrogen chloride, hydrogen fluoride, ammonia, PCDDs, PCDFs, benzene, toluene, xylene, polycyclic aromatic hydrocarbons, chlorobenzenes and PCBs (UNEP, 2004c).

98

It should be noted, however, that cement kilns can comply with PCDD and PCDF air emission levels below 0.1 ng TEQ/Nm3 (UNEP, 2004c) Residues include cement kiln dust captured by the air pollution control system.

Energy requirements: New kiln systems with five cyclone preheater stages and precalciner will require an average of 2,900–3,200 MJ to produce 1 Mg of clinker (UNEP, 2004c). Each ton of cement produced typically requires 60-130 kilograms of fuel oil, or its equivalent, and about 105 KWh of electricity (Loréa, 2007).

Material requirements: Cement manufacturing requires large amounts of materials, including limestone, silica, alumina, iron oxides and gypsum. Portability: Cement kilns are available only in fixed configurations.

Health and safety: Treatment of wastes within cement kilns can be regarded as relatively safe if properly designed and operated.

Capacity: Cement kilns co-incinerating wastes as a fuel are normally limited to a maximum of 40 per cent of the heat requirement in the form of hazardous waste (UNEP, 2004c). It has been noted, however, that cement kilns with high throughput can potentially treat significant quantities of waste.

Chlorides have an impact on the quality of the cement and so have to be limited. Chlorine can be found in all the raw materials used in cement manufacture, so the chlorine levels in the hazardous waste can be critical. However, if they are blended down sufficiently, cement kilns can treat highly chlorinated hazardous waste.

State of commercialization: Cement kilns in the United States of America, some European and a number of developing countries have been used to treat wastes contaminated with POPs (World Business Council, 2004: Formation and Release of POPs in the Cement Industry, Kartensen, 2006).

99

Process description: The GPCR process involves the thermochemical reduction of organic compounds. At temperatures greater than 850°C and at low pressures, hydrogen reacts with chlorinated organic compounds to yield primarily methane and hydrogen chloride.

Efficiency: DEs of 99.9999 per cent have been reported for DDT, HCB, PCBs, PCDDs and PCDFs.

Waste types: In addition to the substances listed above, GPCR should also be capable of treating wastes consisting of, containing or contaminated with all other POPs. GPCR is capable of treating wastes with a high POP concentration, including aqueous and oily liquids, soils, sediments, transformers and capacitors.

Emissions and residues: In addition to hydrogen chloride and methane, low molecular weight hydrocarbons may be emitted. Residues from the GPCR process include used liquor and water. Solid residues will also be generated from solid waste inputs. Since the GPCR process takes place in a reducing atmosphere, the possibility of PCDD and PCDF formation is considered limited.

Release control and post-treatment: Gases leaving the reactor are scrubbed to remove water, heat, acid and carbon dioxide. Scrubber residue and particulate will require disposal off site. Solid residues generated from solid waste inputs should be suitable for disposal in a landfill.

Energy requirements: Methane produced during the process can provide much of the fuel needs. It has been reported that electricity requirements range from 96 kWh per ton of soil treated to around 900 kWh per ton of pure organic contaminants treated.

Material requirements: There is a need for hydrogen supplies, at least during start-up. It has been reported that methane produced during the GPCR process can be

100

used to form enough hydrogen to operate the process thereafter. The hydrogen production unit was plagued, however, by reliability problems in the past. Other material requirements include caustic for the acid scrubber.

Portability: GPCR is available in fixed and transportable configurations.

Health and safety: Use of hydrogen gas under pressure requires suitable controls and safeguards to ensure that explosive air-hydrogen mixtures are not formed. Operating experience gained to date has indicated that the GPCR process can be undertaken safely.

Capacity: GPCR process capacity is dependent on the capacity of the three pre-treatment units, as specified below:

(a) TRBP has a capacity of up to 100 tons of solids per month or up to four litres per minute of liquids. Two TRBPs can be used in parallel to double capacity;

(b) Torbed reactor has a capacity of up to 5,000 tons of soils and sediments per month, although this pre-treatment unit is still in the development stage; and

(c) LWPS has a capacity of three litres per minute.

Other practical issues: Contaminants such as sulphur and arsenic were found to inhibit treatment in earlier development stages, although it is unclear whether this problem is still encountered.

State of commercialization: Commercial-scale GPCR plants have operated in Canada and Australia. The GPCR plant in Australia operated for more than five years until 2000.

101

Process description: Hazardous-waste incineration uses controlled flame combustion to treat organic contaminants, mainly in rotary kilns. Typically, a process for treatment involves heating to a temperature greater than 850°C or, if the waste contain more than 1 per cent halogened organic substances, greater than 1,100°C, with a residence time greater than two seconds, under conditions that assure appropriate mixing and with 6 per cent oxygen. Dedicated hazardous-waste incinerators are available in a number of configurations, including rotary kiln incinerators, and static ovens (for liquids only). High-efficiency boilers and lightweight aggregate kilns are also used for the co-incineration of hazardous wastes.

Efficiency: DREs of greater than 99.9999 per cent have been reported for treatment of POPs wastes. DEs of greater than 99.999 and DREs of greater than 99.9999 per cent have been reported for aldrin, chlordane and DDT (Ministry of the Environment of Japan, 2004), while DEs between 83.15 and 99.88 per cent have been reported for PCBs (EPA, 1990).

Waste types: As noted above, hazardous-waste incinerators are capable of treating all POPs wastes. . Incinerators can be designed to accept wastes in any concentration or any physical form, i.e., gases, liquids, solids, sludges and slurries.

Pre-treatment: Depending upon the configuration, pre-treatment requirements may include blending, dewatering and size reduction of wastes.

Emissions and residues: Emissions include carbon monoxide, carbon dioxide, HCB, hydrogen chloride, particulates, PCDDs, PCDFs and PCBs and water vapour. Incinerators applying BAT, inter alia, designed for high temperature and equipped with prevention of reformation of PCDDs and PCDFs and dedicated PCDD and PCDF removal (e.g., activated carbon filters), have led to very low PCDD and PCDF emissions to air and discharges to water. In the residues, PCDDs and PCDFs are

102

mainly found in fly ash and salt, and to some extent in bottom ash and scrubber water sludge.

Release control and post-treatment: Process gases may require treatment to remove hydrogen chloride and particulate matter and to prevent the formation of and remove unintentionally produced POPs (sulphur and nitrogen oxides, heavy metals and organic micro pollutant such as PAHs, as like as carbon monoxide being also an indicator of combustion efficiency). This can be achieved through a combination of types of post-treatments, including cyclones and multi-cyclones, electrostatic filters, static bed filters, scrubbers, selective catalytic reduction, rapid quenching systems and carbon adsorption. Depending upon their characteristics, bottom and fly ashes may require disposal within a specially engineered landfill.

Energy requirements: The amount of combustion fuel required will depend upon the composition and calorific value of the waste and also upon the flue-gas treatment technologies applied.

Material requirements: Material requirements include cooling water and lime or another suitable material for removal of acid gases and other pollutant like active carbon.

Portability: Hazardous waste incinerators are available in both portable and fixed units.

Health and safety: Health and safety hazards include those associated with high operating temperatures.

Capacity: Hazardous-waste incinerators can treat between 30,000 and 100,000 tons per year.

State of commercialization: There is a long history of experience with hazardous waste incineration.

103

Process description: The Plascon™ process uses a plasma arc with temperatures in excess of 3,000°C to pyrolyse wastes. Together with argon, wastes are injected directly into the plasma arc. The high temperature causes compounds to dissociate into their elemental ions and atoms. Recombination occurs in a cooler area of the reaction chamber, followed by a quench, resulting in the formation of simple molecules.

Efficiency: Bench-scale tests with oils containing 60 per cent PCBs have achieved DREs ranging from 99.9999 to 99.999999 per cent.

Waste types: In addition to PCB oils, a Plascon™ plant in Australia has recently been configured to treat pesticide wastes. Waste types to be treated must be liquid or gas, or solid if in the form of a fine slurry which can be pumped. Very viscous liquids or sludges thicker than 30–40 weight motor oil cannot be processed without pre-treatment. Other solid wastes cannot be treated unless some form of pre-treatment is undertaken.

Pre-treatment: Pre-treatment is not required for most liquids. Solids such as contaminated soils, capacitors and transformers can be pre-treated using thermal desorption or solvent extraction.

Emissions and residues: Emissions include gases consisting of argon, carbon dioxide and water vapour. Residues include an aqueous solution of inorganic sodium salts, such as sodium chloride, sodium bicarbonate and sodium fluoride. Bench-scale tests with PCBs showed PCDD levels in scrubber water and stack gases in the part per trillion (ppt) range. At a Plascon™ plant in Australia, used to treat a variety of wastes, the level of PCBs in the effluent discharged complies with a 2 ppb limit. POP concentrations in solid residues are unknown.

104

Release control and post-treatment: Currently, there is little information available regarding post-treatment requirements.

Energy requirements: A 150 kW Plascon™ unit requires 1,000–3,000 kWh of electricity per tonne of waste.

Material requirements: Currently, there is little information available regarding material requirements. It has been noted, however, that this process does require argon gas, oxygen gas, caustic and cooling water.

Portability: Plascon™ is available in transportable and fixed units.

Health and safety: Since the Plascon™ process has a low throughput, there is a low risk associated with release of partially treated wastes following process failure. Currently, there is little additional information available regarding health and safety.

Capacity: A 150 kW Plascon™ unit can process 1–3 tons per day of waste.

Other practical issues: It should be noted that metals or metal-like compounds (e.g., arsenic) may interfere with catalysts or cause problems in disposing of the residue. For example, arsenicals in pesticide waste exported from Pacific islands for disposal in Australia using the Plascon™ process have presented a particular problem for that project.

State of commercialization: BCD Technologies Pty Ltd. operates two plasma plants in Australia: one in Brisbane for PCBs and POPs and another in Melbourne for treating CFCs and halons. BCD Technologies Pty Ltd. also operates a BCD plant for low-level PCBs and POPs and also has two thermal desorbers for treating contaminated solids. Mitsubishi Chemical Corporation has installed a Plascon™ plant in 2004 in Japan and treated 968 Mg of PCBs for one year.

105

Process description: SCWO and subcritical water oxidation treat wastes in an enclosed system using an oxidant (such as oxygen, hydrogen peroxide, nitrite, nitrate, etc.) in water at temperatures and pressures above the critical point of water (374°C and 218 atmospheres) and below subcritical conditions (370°C and 262 atmospheres). Under these conditions, organic materials become highly soluble in water and are oxidized to produce carbon dioxide, water and inorganic acids or salts.

Efficiency: DEs of greater than 99.999 per cent and DREs of greater than 99.9999 per cent have been reported for aldrin, chlordane and PCBs for SCWO (Ministry of the Environment of Japan, 2004). DEs of greater than 99.999999 and DREs of greater than 99.9999999 per cent have been reported for subcritical water oxidation (Ministry of the Environment of Japan, 2004). DREs as high as 99.9999 per cent have also been demonstrated for PCDDs in bench-scale tests.

Waste types: SCWO and subcritical water oxidation are thought to be applicable to all POPs (Japan Industrial Waste Management Foundation, 2005). Applicable waste types include aqueous wastes, oils, solvents and solids with a diameter of under 200 µm. The organic content of the waste is limited to below 20 per cent.

Emissions and residues: During laboratory-scale PCB destruction, it was shown that the SCWO technology has the potential to form high concentrations of PCDFs (in the per cent range) during PCB degradation even at temperatures of practical operation (Weber, 2004). It has been reported that emissions contain no oxides of nitrogen or acid gases such as hydrogen chloride or oxides of sulphur and that process residues consist of water and solids if the waste contains inorganic salts or organic compounds with halogens, sulphur or phosphorus. Limited information has been reported regarding potential concentrations of undestroyed chemicals. The process is designed so that emissions and residues can be captured for reprocessing if needed.

106

Release control and post-treatment: Currently, there is no specific information available regarding post-treatment requirements.

Energy requirements: Energy requirements are expected to be relatively high because of the combinations of high temperatures and pressures. It has been claimed, however, that as long as relatively high hydrocarbon content is present in the feed, no energy input is required to heat the feed to supercritical temperatures.

Material requirements: The SCWO and subcritical water oxidation reaction vessel must be constructed of materials capable of resisting corrosion caused by halogen ions. Material corrosion can be severe at the temperatures and pressures used in the SCWO and subcritical water oxidation process. In the past, the use of titanium alloys has been proposed to tackle this problem. Current vendors claim to have overcome this problem through the use of advanced materials and engineering designs.

Portability: The SCWO and subcritical water oxidation units are currently used in a fixed configuration, but are thought to be transportable.

Health and safety: The high temperatures and pressures used in this process require special safety precautions.

Capacity: Current SCWO demonstration units are capable of treating 500 kg/h, while full-scale units will be designed to treat 2,700 kg/h.

Other practical issues: Earlier designs were plagued by reliability, corrosion and plugging problems. Current vendors claim to have addressed these problems through the use of special reactor designs and corrosion-resistant materials.

State of commercialization: A full-scale commercial plant having capacity of 2 mg per day was installed in 2005 and now in operation in Japan. In addition, the SCWO process has been approved for full-scale development and use in the chemical-weapon destruction programme of the United States of America.

107

Process description: The processes described below are primarily designed for the recovery of iron and non-ferrous metals (NFM) e.g. aluminium, copper, zinc, lead and nickel from ore concentrates as well as from secondary raw materials (intermediates, wastes). However, due to the nature of the processes they are in some cases also used on a commercial basis for the destruction of the POP content of appropriate wastes. A general description of some of the following processes may also be found in the European BAT reference documents:

(a) Processes which are relevant for the destruction of the POP content in iron-containing wastes use certain types of blast furnace, shaft furnace or hearth furnace. All these processes operate under reducing atmospheres at high temperatures (1,200°C–1,450°C). The high temperature and the reducing atmosphere destroy PCDDs and PCDFs contained in the wastes and avoid de novo synthesis. The blast furnace and the shaft furnace processes use coke and small amounts of other reducing agents to reduce the iron-containing input to cast iron. There are no direct emissions of process gas as it is used as a secondary fuel. In the hearth furnace process, the iron-containing material is charged to a multi-hearth furnace together with coal. The iron oxide is directly reduced to solid direct reduced iron (DRI). In a second step the reduced iron is melted in an electric arc furnace to produce cast iron;

(b) Processes which are relevant for the destruction of the POP content in wastes containing NFMs are the Waelz rotary kiln process and bath melting processes using vertical or horizontal furnaces. These processes are reductive, reach temperatures of 1,200°C and use rapid quenching thus PCDDs and PCDFs are destroyed and de novo synthesis is avoided. In the Waelz process zinc-containing steel mill dusts, sludges, filter cakes, etc. are pelletized and smelted together with a reductant. At temperatures of 1,200°C, the zinc volatizes and is oxidized to “Waelz Oxide”, which is collected in a filter unit. In the vertical bath furnace process, copper-containing residues are smelted at temperatures of at least 1,200°C. The filter dust is used for the production of zinc and zinc compounds. In the horizontal bath furnace process,

108

lead-containing residues and ore concentrates are charged continuously into a smelting bath which has an oxidizing and a reducing zone with temperatures between 1,000°C and 1,200°C. The process gas (sulphur dioxide concentration above 10 per cent) is used for sulphuric acid production after heat recovery and de-dusting. The dust from the process is recycled after cadmium leaching.

Efficiency: Data on DE or DRE are not available.

Waste types: The processes described above are specific to the treatment of the following wastes:

(a)Residues from iron- and steel-making processes such as dusts or sludges from gas treatment or mill scale that may be contaminated with PCDDs and PCDFs;

(b)Zinc-containing filter dusts from steelworks, dusts from gas cleaning systems of copper smelters etc. and lead-containing leaching residues of NMF production that may be contaminated with PCDDs and PCDFs.

Pre-treatment: Iron-containing materials recycled by the conventional blast furnace process require pre-treatment in an agglomeration plant. For the shaft furnace (“Oxycup” furnace) process the iron-containing waste is briquetted. This is a cold process in which a binder and water is added to the fines, which are then pressed to briquettes, dried and hardened. Generally no pre-treatment is necessary for the multi-hearth furnace process, although under in some special cases the fine solids may have to be pelletized. This involves only the addition of water and the formation of pellets in a drum. Special pre-treatment of materials contaminated with POPs is not usually necessary for NFMs.

Emissions and residues: In iron and NFM production PCDDs and PCDFs may be formed within the process or downstream in the flue gas treatment system. Application of BAT should, however, prevent or at least minimize such emissions. Where the processes described above are used for the destruction of the POPs content in wastes appropriate release control and post-treatment techniques are required. When such techniques are employed, air emissions of PCDDs and PCDFs from these processes are below 0.1 ng TEQ/Nm3. Slags are in many cases used for construction purposes. For iron metals, emissions can occur from pre-treatment in an agglomeration plant and also in the off-gas from the melting furnace. Residues from de-dusting systems are mainly used in the NFM industry. The off-gas of the multi-hearth furnace is de-dusted by a cyclone, underlies a post-combustion, is quenched and cleaned by addition of adsorbent and a bag filter. The off-gas of the melting furnace also underlies a post-combustion and is quenched before it is mixed up with the off-gas of the multi-hearth furnace for the joint adsorbance step. For NFMs, residues include filter dusts and sludges from waste water treatment.

Release control and post-treatment: Control of temperatures and rapid quenching are often suitable means of minimizing PCDD and PCDF formation. Process gases require treatment to remove dust which consists mainly of metals or metal oxides as well as sulphur dioxide when smelting sulphidic materials. In the ferrous metals industry waste gases from agglomeration plants are treated by an electrostatic precipitator followed by further flue gas treatment, e.g., adsorption techniques followed by an additional bag filter. The off-gases from multi-hearth furnaces are de-dusted by a cyclone and subjected to treatment by post-combustion, quenching and further cleaning by addition of adsorbent followed by a bag filter. The off-gases from the associated melting furnaces also require post-combustion and quenching and are then combined with the off-gas stream from the multi-hearth furnaces for further treatment by addition of absorbent followed by a bag filter. In NFM production

109

suitable treatment techniques include, inter alia, the use of fabric filters, electrostatic precipitators or scrubbers, sulphuric acid plants or adsorption techniques with activated carbon.

Energy requirements: Production processes for iron and NFM are energy-intensive with significant differences between different metals. The treatment of the POP content in wastes within these processes requires little additional energy.

Material requirements: For production of metals, raw materials (ores, concentrates or secondary material) are used as well as additives (e.g., sand, limestone), reductants (coal and coke) and fuels (oil and gas). Temperature control to avoid de novo synthesis of PCDDs and PCDFs requires additional water for quenching.

Portability: Metal smelters are large and fixed installations.

Health and safety: The treatment of wastes within thermal processes can be regarded as safe if properly designed and operated.

Capacity: Metal smelters described above have feedstock capacities above 100,000 tonnes per year. Current experience with the addition of wastes contaminated with POPs to the feedstock involves much smaller quantities but the capability for treating larger quantities may well exist and is being explored.

110

Process description: Plasma melting decomposition method is used as the thermal destruction method of solid waste containing or contaminated with PCB. Solid waste containing or contaminated with PCBs is canned directly into containers such as drums or pails without shredding or disassembling. In the plasma furnace, plasma torch generates high temperature plasma gas (air) so that the furnace temperature is maintained to melt the waste together with the container itself. All the organic substances including PCB is decomposed to CO2, H2O and HCl under the high temperature condition in the plasma furnace, and inorganic materials including metals are oxidized to become molten slag. The plasma furnace exceeds 1,400˚C (Tagashira et al., 2006).

Efficiency: In Japan, a pilot Plasma waste converter plant was tested for PCB treatment in 2006. The result showed that destruction efficiencies (DEs) ranged from 99.9999454% to 99.9999997% and destruction removal efficiencies (DREs) ranged from 99.9999763% to 99.9999998% (Tagashira et al., 2006).

Waste types: In commercial scale plants in Japan, named the JESCO Plasma Melting treatment facility, Japan Environmental Safety Corporation (JESCO) claims that this facility can be applied to the treatment of solid waste containing or contaminated with PCB such as fluorescent light ballasts, sludge, carbonless paper and secondary contaminants (JESCO 2009).

Pre-treatment: In commercial scale plant in Japan, the containers such as drums or pails in PCB-contaminated waste mixed with basicity controlling agents like lime stone or silica sand as needed are pushed into the plasma furnace (JESCO 2009).

Emissions and residues: Air emission levels of dioxins were 0.0000043-0.068 ng TEQ/Nm3 in a pilot scale plant (Tagashira et al., 2006). Together with an enhanced gas treatment system, dioxins emission level can be controlled within a range of 0.00001-0.001ng TEQ/Nm3 (Tagashira et al., 2007). The JESCO Plasma Melting

111

treatment facility can comply with dioxins air emission levels below 0.1 ng TEQ/Nm3

(JESCO 2009).

Release and control and post-treatment: In Japan, as exhaust gas pollution control, 2-stage bag filter with lime and pulverized activated carbon injection removes dust, acid gas such as HCl and SOx and dioxins, and catalyst tower with NH3 gas injection removes NOx. At the last stage, activated carbon is installed (Tagashira et al., 2006).

Material requirements: PWC was reported that lime and pulverized activated carbon supply is required (Tagashira et al., 2006). To improve molten slag fluidity basicity controlling agents such as silica sand or lime stone are also required when it’s needed.

Portability: PWC is available only in fixed units in Japan (JESCO 2009).

Capacity: In Japan, it has been demonstrated that the two JESCO Plasma Melting treatment facilities are capable of treating 10.4 tons and 12.2 tons of waste per day (waste containing PCB contaminants volume) (JESCO 2009, JESCO 2013).

State of commercialization: In Japan, the JESCO Plasma Melting treatment facility in Kitakyushu using PWC Technology treatment of 10.4 tons of waste PCB per day has been on commercial scale since July 2009 (JESCO 2009) and the same type of facility having capacity of 12.2 tons of PCB waste per day in Hokkaido is under trial run to commence commercial operations from autumn of 2013(JESCO 2013).

112

Where neither destruction nor irreversible transformation is the environmentally preferable option, for wastes with a POP content above the low POP content countries may allow such wastes to be disposed of by other methods.

Wastes containing or contaminated with POPs where such other disposal methods may be considered include:

(a) Waste from power stations and other combustion plants (except those listed in subparagraph (d) below), wastes from the iron and steel industry and wastes from aluminium, lead, zinc, copper and other non-ferrous thermal metallurgy. These include bottom ash, slag, salt slags, fly ash, boiler dust, flue-gas dust, other particulates and dust, solid wastes from gas treatment, black drosses, wastes from treatment of salt slags and black drosses, dross and skimmings;

(b) Carbon-based and other linings and refractories from metallurgical processes;(c) The following construction and demolition wastes:

(i) Mixtures of, or separate fractions of, concrete, bricks, tiles and ceramics;(ii) The inorganic fraction of soil and stones, including excavated soil from

contaminated sites;(iii) Construction and demolition wastes containing PCBs, excluding equipment

containing PCBs; (d) Wastes from the incineration or pyrolysis of waste, including solid wastes from

gas treatment, bottom ash, slag, fly ash and boiler dust; (e) Vitrified wastes and waste from vitrification, including fly ash and other flue-gas

treatment wastes and non-vitrified solid phase wastes.

The relevant authority of the country concerned should be satisfied that neither destruction nor irreversible transformation of the POP content, performed according to best environmental practice or best available techniques, is the environmentally preferable option.

113

Other disposal methods when neither destruction nor irreversible transformation is the environmentally preferable option include those described below.Specially Engineered Landfill

Any landfilling should be carried out in a way that minimizes the potential of the POPs content to enter the environment. This may be achieved by pre-treatment, e.g., a suitable solidification process. A specially engineered landfill should comply with requirements as regards location, conditioning, management, control, closure and preventive and protective measures to be taken against any threat to the environment in the short- as well as in the long-term perspective, in particular as regards measures against the pollution of groundwater by leachate infiltration into the soil. Protection of soil, groundwater and surface water should be achieved by the combination of a geological barrier and a bottom liner system during the operational phase and by the combination of a geological barrier and a top liner during the closure and post-closure phase. Measures should be taken to reduce the production of methane gas and to introduce landfill gas control. Landfill leachate treatment technologies should be in place to reduce and prevent toxic leachate to enter into the environment. In addition, a uniform waste acceptance procedure on the basis of a classification procedure for waste acceptable in the landfill, including in particular standardized limit values, should be introduced. Moreover, monitoring procedures during the operation and post-closure phases of a landfill should be established in order to identify any possible adverse environmental effects of the landfill and take the appropriate corrective measures. A specific permit procedure should be introduced for the landfill. Permits should include specifications regarding types and concentrations of wastes to be accepted, leachate and gas control systems, monitoring, on-site security, and closure and post-closure.

The following wastes containing or contaminated with POPs are not suitable for disposal in specially engineered landfills:

(a) Liquids and materials containing free liquids;(b) Biodegradable organic wastes;(c) Empty containers, unless they are crushed, shredded or similarly reduced in

volume;(d) Explosives, flammable solids, spontaneously combustible materials, water-

reactive materials, oxidizers, organic peroxides, corrosive and infectious wastes.

Permanent storage in underground mines and formations

Permanent storage in facilities located underground in geohydrologically isolated salt mines and hard rock formations is an option to separate hazardous wastes from the biosphere for geological periods of time. A site-specific security assessment according to pertinent national legislation such as the provisions contained in appendix A to the annex to European Council decision 2003/33/EC of 19 December 2002 establishing criteria and procedures for the acceptance of waste at landfills pursuant to article 16 of and annex II to directive 1999/31/EC should be performed for every planned underground storage facility.

Wastes should be disposed-off in a manner that excludes any undesirable reaction between different wastes or between wastes and the storage lining, among other things by storing in chemically and mechanically secure containers. Wastes that are liquid, gaseous, emit toxic gases or are explosive, flammable or infectious should not

114

be stored underground in mines. Operational permits should define waste types that should be generally excluded.

The following should be considered in the selection of permanent storage for disposal of POPs wastes:

(a) Caverns or tunnels used for storage should be completely separated from active mining areas and areas that maybe reopened for mining;

(b) Caverns or tunnels should be located in geological formations that are well below zones of available groundwater or in formations that are completely isolated by impermeable rock or clay layers from water-bearing zones;

(c) Caverns and tunnels should be located in geological formations that are extremely stable and not in areas subject to earthquakes.

Other disposal methods when the POP content is low

If wastes containing or contaminated with POPs at concentrations under the low POP content are not disposed of with the methods described above, they should be disposed of in accordance with pertinent national legislation and international rules, standards and guidelines, including the specific technical guidelines developed under the Basel Convention.

115

116

Emergency response plans should be in place for all POPs in production, in use, in storage, in transport or at disposal sites. While the emergency response plans can vary for each situation and each type of POP, the principal elements of an emergency response include:

(a) Identifying all potential hazards, risks and accident events; (b) Identifying relevant local and national legislation governing emergency

response plans;(c) Planning for anticipated emergency situations and possible responses;(d) Maintaining a complete up-to-date inventory of all POPs on site;(e) Training personnel in response activities, including simulated response

exercises and first aid;(f) Maintaining mobile spill response capabilities or retaining the services of a

specialized firm for spill response;(g) Notifying fire services, police and other government emergency response

agencies of the location of POPs and the routes of transport;(h) Installing mitigation measures such as fire suppression systems, spill

containment equipment, fire-fighting water containment, spill and fire alarms and firewalls;

(i) Installing emergency communication systems including signs indicating emergency exits, telephone numbers, alarm locations and response instructions;

(j) Installing and maintaining emergency response kits containing sorbents, personal protective equipment, portable fire extinguishers and first aid supplies;

(k) Integrating facility plans with local, regional, national and global emergency plans, if appropriate;

(l) Regular testing of emergency response equipment and review of emergency response plans.

Emergency response plans should be prepared jointly by interdisciplinary teams that include emergency response, medical, chemical and technical personnel and also representatives of

117

labour and management. When applicable, representatives of potentially impacted communities should also be included.

118

Poor handling, storage and disposal practices in particular may lead to releases of POPs at sites, resulting in contamination of the site with high levels of POPs that may pose serious health concerns. In general, there are three main ways to protect workers and members of the public from chemical hazards (in order of preference):

a. Keep workers and members of the public away from all possible sources of contamination;

b. Control the contaminants so that the possibility of exposure is minimized;c. Protect workers by ensuring that personal protective equipment is used.

This necessitates the notification of Safety Officer(s)/Manager(s) for the arrangements of following:

a. Capacity building of the personnel on understanding the issuesb. Development of Health and Safety Planc. Arrangement of the Personal Protective Equipmentd. Training of workerse. Supervise and ensure that the health and safety plan is implementedf. Ensure that handing, storage and disposal is carried out in accordance with the

requirements of Stockholm Convention and international best practicesg. Regular monitoring and reporting of the activities

Health and safety plans should be in place at all facilities that handle POPs wastes to ensure the protection of everyone in and around the facility. The health and safety plan for each specific facility should be developed by a trained health and safety professional i.e. the notified Safety Officer/Manager with experience in managing the health risks associated with the specific POPs at the facility.

All health and safety plans should adhere to the above principles and recognize local or national labour standards. Most health and safety programmes recognize various levels of

119

safety, with risk levels depending on the site in question and the nature of the contaminated materials found there. The level of protection provided to workers should correspond to the level of the risk to which they are exposed. Levels of risk should be established and each situation should be evaluated by the notified Safety Officer/Manager.

120

Personal protective equipment (PPEs) is important for safeguarding the health of workers at POPs sites. Provision of PPEs should be made part of the Health and Safety Plan. The Health and Safety Planning for POPs site must have provisions for PPEs such as:

a. Respiratory aid like Gas Masksb. Impermeable head cap/hatc. Impermeable body cover fabric i.e. coverall with hood and face shieldd. Glovese. Full body suitf. Impermeable Bootsg. Gogglesh. Personal decontamination materialsi. Site clean-up kit

121

A good Health and Safety Plan should include the following:

Contact details of relevant department to contact in case of emergency such as of Fire Department, Rescue Services, Hospital, Ambulance, Police, etc.

Storage of PPEs and clothing in an easy accessible location but enough away from POPs, dusts, fumes, etc.

Provision of clean water along with eye washing facility for emergency. A first aid kit with soap or hand sanitizer. Working tools such as shovel, dustpan, broom and absorbent materials like sawdust,

clay, etc. to clean the spills if any. Provision for training of workers on PPEs.

122

123