2.1.1       Work Plan

The survey and testing for Arsenic mitigation program was conducted in Taluka Khairpur, Kotdiji and Gambat (District Khairpur) and Dadu, Johi and Sehwan Talukas (District Dadu). In all sixty-seven (67) Union Councils of these Tehsils were covered in the survey. Following steps were taken in the survey:

• The information of the work was disseminated to the Zila (District) Nazims and District Coordination Officers (DCOs) of Districts Khairpur and Dadu.

• Meetings were convened with the following officials with regard to implementation of the program:

• Through these meetings effective coordination was made with all related individuals and organizations.

• Trainings were imparted at Taluka and Union Council.

• After trainings, volunteers convened meetings at village level.

• Merck field kits were provided for testing the water sources

• Supervision and monitoring by Secretaries of Union Councils, Taluka Municipal Officers and District Monitors.

• 10% validation of samples from each Union Council through Pakistan Council of Research in Water Resources (PCRWR), Islamabad.

• Data regarding the presence of other parameter like Manganese, Iron, period of installation of sources, users of sources, depth of sources and surroundings of water sources were also collected.

2.1.2 Limitations

The field team during the survey faced the following limitations;

• At some places work delayed as desired cooperation could not be received due to personal and political differences and illiteracy rate aspect among Nazims and Councilors of Union Councils. Consequently, teachers and representatives of NGOs were involved in the survey.

• In some villages, law and order situation such as kidnapping, robbery and snatching of vehicles/ motorcycles was very common; therefore, the volunteers were reluctant to go in those areas.

• Female participation was negligible due to illiteracy among the women, social and religious customs and trends and presence of their relatives and neighbour in the meetings.

• Most of the local people believed that team was conducting research for oil and gas exploration and some of them were of the opinion that survey was being conducted to impose taxes on their water resources.

2.1.3. Trainings

The field team imparted trainings at Taluka and Union Council level in their respective offices. In all 1,635 persons participated in 67 training events.

Table-1: Details of Trainings at UC level by SAFWCO team.

2.1.3.1 Training Objectives

Trainings were organized in Taluka and Union Council Offices in all sixty seven Union Councils of six Talukas and Khairpur and Dadu districts with the objectives to:

• To create awareness about the Drinking Water Quality Survey for arsenic mitigation program including arsenic and its effects on human health

• To ensure involvement of Union Council Nazims, Secretaries, Counselors and Community activists in the awareness and water testing program in their respective areas.

• To introduce the Merck field kits, its usage, procedure of testing and precaution of testing.

• To explain the roles and responsibilities of Taluka Municipal Officers and Union Councils Secretaries, Councilors and Community Activists.

• To develop a plan of Action of trainings at Union Council level to impart trainings smoothly and properly.

2.1.3.2 Training Description

The facilitator briefed the participants about aims and objectives of the organizations (SAFWCO and UNICEF) and their roles to conduct drinking water quality survey and evaluate the presence of arsenic in the drinking water. Welcoming the participants Taluka Nazims appreciated UNICEF initiative in water testing and importance of water for health. They advised all the Nazims, Naib Nazims, Secretaries, Counselors, CBOs, NGOs and social workers to extend their full cooperation with the SAFWCO team for the completion of this important task with interest and devotion. They themselves assured their full cooperation in this regard. The purpose of implementation of this program was to know about the presence of Arsenic in drinking water and develop mitigation measures.

Resource persons mentioned that initially meetings were conducted at District Administration level and subsequently at Taluka and Union Council levels, where the program awareness was conveyed, testing procedure explained and action plan developed to implement the program.  The testing which was to be conducted by the community activists was easy.  The single test takes 30 minutes and each Merck kit  is used for  testing of 100 water samples from various drinking water sources such as handpump, tube well, well and Water supply. The procedure of water testing through Arsenic Merck field kit was explained clearly in order to orient and familiarize the participants about the procedure of testing, and the material to be used. Awareness material, posters, hand bills, guidelines for testing were distributed among the participants. Description on the effects of long term ingestion of arsenic contaminated water was also given to the participants.

Discussion of resource person with community representatives

Resource person also briefed that each and every source will be marked by writing sample number and corresponding code number in the following manner:

• KHP-OO1        - 1^st sample taken from the source from Khairpur district.

• DU-008            - 8^th sample taken from the source of Dadu district. .

All the information regarding source and testing will be collected on already designed profarma having source information, name of village, name of source (hand pump, tube well, well or water supply), depth of source, year of installation and number of household using the source. Information regarding sample results including start time, finish time, sample results, distance from previous source, code number, and source owner/care taker were also to be recorded. It was also explained to get information on other parameters like presence of manganese and iron stains, color, taste, odour of water and information about surrounding source. The name of person who would conduct the test, his/her designation, organization and signature should also appear on the survey form.

2.1.3.3    The Participants

In all 1,755 persons of following categories participated in Taluka and Union Council training programs:

• Nazims and Naib Nazims

• Counselors and Secretaries

• NGOs and CBOs

• Village Volunteers

• Doctors and Health Technicians

• Teachers

• Citizen Community Board Members

• Scouts

Details of the participants at UC level are given in Annex-I

2.1.4. Water Sample Testing Procedure

The procedure to use the field kits (Merck kit), their package, and procedure adopted in the field by the volunteers is presented below.

Site identification of source

2.1.4.1        Use of Field Kits (Merck Kit)

The following methodology was adopted in using the field kits (Merck Kit) to test the samples:

• Testing was performed at the source (tube well, hand pump etc.)

• First, the tube well or hand pump was run for couple of minutes to get the water from the bottom of the well and sample was collected in a plastic container and tested by using Merck Field Kit

2.1.4.2        Package Contents of the Merck Kit Box

Merck kit box contained the following items;

• Packet containing 100 analytical test strips

• One bottle of reagent As-1 and two bottles of reagent As-2

• One reaction vessel with stopper

• 110-ml plastic syringes

• One measuring spoon

2.1.4.3    Procedure for Sample Collection

• The following procedure was adopted in the collection of water samples:

• Removed 1 analytical strip and immediately reclosed the packet.

• Inserted the strip in the reaction vessel stopper in such a way that the reaction zone was halfway in the vessel. By means of syringe, transferred 10 ml of solution (water sample) to be tested into reaction vessel and added two measuring spoons of reagent As-1

• Rapidly added 10 drops of reagent As-2, immediately closed the reaction vessel with the stopper and swirled gently. The sample solution was not allowed to come into contact with the test strips.

• Left the reaction vessel for 30 minutes gently swirling two or three times.

• Removed the test strip, briefly dipped into water, shacked off excess liquid and determined with which color the reaction zone coincides with.

Sampling and analysis at the source

2.1.5 Sample Distribution and Water Sources

In all 20,158 samples were collected from 67 Union Councils of six (06) Talukas of Khairpur and Dadu Districts in Sindh. The samples were collected from four sources viz: hand pumps, tube wells, wells and water supply. Majority of the sources (96 per cent) are hand pumps, whereas only three (03) percent are wells. The distribution of water sources is presented in the following table.

Table-1.1: Distribution of Water Sources Analyzed by SAFWCO

2.1.6.      Analysis of Data

All the data was entered in the Microsoft Excel software and analysis was made using Statistical Package for Social Scientists (SPSS).

2.2. Sampling Size

Water samples for evaluation of arsenic were collected from Khairpur Mirs and Dadu districts and analysed with help of Field testing Kits by the field staff of SAFWCO and Local Government. Ten percent of the total water samples collected by SAFWCO were sent to PCRWR for lab analysis.

Table-1.2: Distribution of Water Sample Analysed by PCRWR.

2.3 Sample Collection and Preservation

Water samples were collected by the field teams of SAFWCO in ½ liter polyethylene bottles according to standard methods. A distance of half kilometer was maintained between the two sampling points. The preservative (1% concentrated HCl) was used in the samples collected for arsenic analysis.

2.4 Method of Analysis

Three analytical methods for inorganic arsenic analysis are reported in standard Literature. These methods are; 1) Atomic Absorption Spectrometric (AAS) method, 2) Silver Diethyldithiocarbamate method and 3) Inductive Coupled Plasma (ICP) Spectrophotometric method. Atomic Absorption Spectrophotometer (Hydride Generation mode) was used for the analysis of arsenic in water samples. All samples were analysed on HS 55 Mercury/Hydride system, an accessory (AAS, Vario 6 Analytik Jena AG) for the matrix free determination of the hydride forming elements such as As, Bi, Sb, Se, Sn and Te. The Hydride technique makes use of fact that hydrogen liberated in the reaction of the weakly acidic sample solutions with sodium boro-hydride which combines with metal ions to form gaseous hydrides. These are carried to the hot quartz cell by the carrier gas and decomposed by collision processes in a series of steps, until free As atoms were obtained.

2.4.1    Equipment and Apparatus

For the analysis of arsenic, Atomic Absorption Spectrophotometer (AAS Vario 6 Analytik Jena AG), Mercury/Hydride System HS55 (Analytik Jena AG), and Argon Gas with 99.99% purity were used.

2.4.2    Reagents and Their Preparation

The following common reagents were used for the analysis;

• Sodium borohydride (NaBH_4, 98% purity)

• Sodium hydroxide, NaOH

• Hydrochloric Acid (Concentrated 37% HCl)

• Arsenic Standard (1007 mg/ml, As in 2% HNO_3, BDH)

In order to make reducing solution (Reductant), 15 gram sodium borohydride (NaBH₄) and 5 gram of sodium hydroxide were dissolved in 500 ml distilled water. This reagent was used as reducing agent for Arsenic analysis.

2.4.3    Procedure of Analysis

The HS 55 Mercury/Hydride system consisting of a basic unit and the cell unit was operated and controlled from PC. Basic unit consists of three accessories. These include batch module, single channel-peristaltic pump and gas valve box. The gas valve box supplied argon gas for scavenging and for transporting the metal hydrides to the system.

Mercury Hydride System of Atomic Absorption Spectrophotometer (AAS)

Pressure of the argon gas cylinder was adjusted at 3-5 bars. After attaining the necessary temperature (950 ^oC) reducing agent was fed by the peristaltic pump. A 10 ml sample was taken into reaction cell and 0.8 ml of concentrated HCl was dispensed into sample and reaction cell was adjusted properly at its place. Calibration standards of arsenic with concentrations (0,10,20,30,40,50 ppb) and (50,60,70,80,90,100 ppb) were prepared. New method of calibration was developed using these standards under the operation of software, and then the method developed was loaded for analysis of actual samples. HS 55 hydride system analyzed the water samples in the following sequences:

• Pre-wash time

• Reaction time

• Rewash time

The detection limit of this method is 0.1 ppb.

Sample Induction in the Reaction Cell of Mercury Hydride System of AAS

2.5          Quality Control Measures

Strict quality control measures were observed in the laboratory by adopting calibration of instruments with known standards and reproducibility checks. Instrument was calibrated with multiple arsenic standards using standard stock solution. The standard stock solution was certified by BDH laboratory supplies LE 17 4XN England. According to certificate of analysis, standard was prepared gravimetrically to contain the elemental concentration of 1007 ppb. The solution was assayed titrimetrically and also concentration was verified by Inductive Coupled Plasma Spectrophotometer (ICP). All the glassware used for preparation of standard solution were acid washed with 1:1 HCl and rinsed three times with deionized water prior to use. Deionized water used for analytical work was freshly prepared having EC of >19 Mohm/cm.

Calibration was evaluated by the value of R² (Degree of fitness) between concentration and absorbance i.e. 0.9995356. After calibration, the analysis of all ground water samples was carried out. During arsenic analysis, a blank and a known arsenic standard was run after every 10 samples for accuracy assurance. After every 10 samples, one pre-analyzed sample was rechecked randomly for reproducibility evaluation. So 10.02% samples were rechecked and results showed the %age of reproducibility less than 10% which is recognized internationally within the range of quality control standards. Furthermore, sample having concentration greater than 50 ppb were also re-checked for confirmation. The results are presented at Annexure-IV. The results of blank and standards run after every 10 samples are given at Annexure-II and reproducible samples results are at Annexure-III.

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