TECHNICAL REPORT WC/96/7R

Report of Field Visit and Initial Data from Investigations into the Prediction and Remediation of Human Selenium

Imbalances in Enshi District, Hubei Province, China 8-26 November 1995.

Fiona M Fordyce

British Geological Survey

TECHNICAL REPORT WC/96nR Overseas Geology Series

Report of Field Visit and Initial Data from Investigations into the Prediction and Remediation of Human Selenium Imbalances in Enshi District, Hubei Province, China 8 - 26 November 1995.

Fiona M Fordyce

A report prepared for the Overseas Development Administration under the ODA/BGS Technology Development and Rescarch Programme, Projcct R-6227: Prediction and Remediation of Human Selenium Imbalanccs.

Bibliographic Reference: F M Fordyce. 1996. Report ofl.’ield Visit c i n d Iiiitial Dum fiom In vestigcrtinns into the Prediction and Riwircliution of H u m m Selenium Iinbalunces in Enshi District, Hubri Province, China. 8 - 26 November 199s.

ONERC 1996

British Geological Survey, Keyworth, Nottingham, 1996.

CONTENTS

LIST OF FIGURES 3

LIST OF TABLES 3

1. ABBREVIATIONS USED IN THIS REPORT 4

2. SCHEDULE 4

3. INTRODUCTION 6

4. PHYSIOGRAPHY, GEOLOGY AND SOILS 9

5 . PUBLIC HEALTH DATA 11

6. LOGISTICS OF THE FIELDWORK PROGRAMME 11

7. SAMPLE COLLECTION 7.1 Soil Sampling

7. I . 1 Suinpling Str[irrgy 7. I . 2 Collrctiorz

7.2 Grain Sampling 7.2. I Sunipling Strute8.y 7.2.2 Collection

7.3 Water Sampling 7.3. I Suniplin'q Str(r1eg.v 7.3.2 Collectiorl

7.4 Hair Sampling 7.4. I Sumpliiig Strutegy 7.4.2 Collection

7.5. I Tobucco 7.5.2 Pig Huir

7.5 Other samples

13 13 13 14 14 15 15 15 16 16 17 17 17 18 18 18

8. SUMMARY OF MEETINGS 18 8.1 Initial meeting with the IRMA on 9/11/95. 18 8.2 Initial mwting with Enshi Local Government Officials on 11/11/95. 19 8.3 Meeting with Enshi Coal Bureau to discuss the Se fertiliser project 20

on 20/1 1/95.

Meeting with the Burcau of'Gcology and Mineral Resources of Hubei Province on 22/1 1/95.

8.4 Meeting with Enshi Public Health Department on 21/11/95. 22

8.6 Concluding meeting with the IRMA on 24/11/95. 34

8.5 34

9. REFERENCES 37

10. ACKNOWLEDGEMENTS 38

APPENDIX A. Details of thc Ficld Sampling Tcam. 39

APPENDIX B. Summary Data for thc 15 Villages. 42

APPENDIX C. Soil Sample Lists and Summary Data. a) Listed by village nainc.

43 43

I

b) Listed by sample number. 46

APPENDIX D. Grain Sample Lists and Summary Dab. a) Listed by village name. b) Listed by sample number.

APPENDIX E. Water Sample Lists and Summary Dab. a) Listed by village name. b) Listed by sample number.

APPENDIX F. Hair Sample Lists and Summary Data a) Listed by village name. b) Listed by sample number.

List of Sampling Equipment. APPENDIX G.

APPENDIX H. Water Chemistry Proccdures for Equipment Listed in Appendix G. pH and Temperature Rcdox Poknlial Bicarbonate Concentration Conductivity

49 49 52

55 55 56

57 57 60

63

65

65 66 67 68

2

LIST OF FIGURES

Figure 1. Figure 2.

Figure 3. Figure 4.

Figure 5. Figure 6.

Figure 7.

Figure 8.

Figure 9. Figure 10. Figure 11. Figure 12.

Figure 13. Figure 14. Figure 15. Figure 16. Figure 17.

Figure 18.

Figure 19. Figure 20.

Figure 2 1 .

KD incidence belt in China Map of Enshi District showing the 15 villages sampled during the present study. Two idealised soil profiles from the Enshi sampling area. Distribution of KD disease in the 14 village meas of Chang Ping community, Lichuan County. Number of KD cases in each year 1969 - 1983 in Lichuan County. Percentage of KD cases occurring in each month of the year in Lichuan County. Percentage KD cases who died over an 11 year period in Lichuan County. Villages sampled in the Enshi Public Health Department Se toxicity investigation. Se content of various components of the Enshi coalstone. Se content of coalstone in various counties in Enshi District. Se content of air through time during the burning of a coalstone fire. Se concentration in soil before and during the burning of a coalstone fire. Se content with depth of a soil profile. Distribution of Se toxicity in various villages. Number of cases of Se toxicity by year. Number of cases of Se toxicity from 1923-1983. Symptoms of Se toxicity in a statistically sampled population of 180 from Se toxicity villages in Enshi District. Symptoms of Se toxicity in a statistically sampled population of 180 from Se toxicity villages in Enshi District. Se concentration in various organs and tissues of a pig. Se concentration in various sample types taken from Yu Tang Ba village in 1981. Se concentration in corn and soil at Yu Tang Ba village in 1963 and 1988.

LIST OF TABLES

Table 1. Latitude and longitude of the main cities in the counties of Enshi District sampled during the field programme and of the Province capital, Wuhan. Geological strata underlying villages sampled in Enshi District. Results of chemical analysis of the Enshi Se fertiliser. KD incidence in selectcd villages in Lichuan county 1969 - 1983.

Table 2. Table 3. Table 4.

3

1. ABBREVIATIONS USED IN THIS REPORT

AGG AFS BA BGS CAGS GSH-PX HPLC ICP-MS IDD IRMA KD LHR LOI MFS NERC ODA TDR UK

Analytical Geochemistq Group Atomic Fluorescence Specrrometry British Airways British Geological Survey Chinese Academy of Geological Sciences Glutathione- peroxidase High Precision Liquid Chromatography Inductively Coupled Plasma Mass Spectrometry Iodine deficiency disorders Institute of Rock and Mineral Analysis Keshan Disease London Heathrow Loss on Ignition Mass Fluorescence Spectrometry Natural Environmental Research Council Overseas Development Agency Technical Development and Research United Kingdom

2 . SCHEDULE

8/11/95

9/11/95 am

Pm

10/11/95

11/11/95 am

Pm

Depart BGS 11 15 travel by hire car to LHR, arrive 1330. Depart LHR 1645 on flight BA039 to Beijing. Arrive Beijing 1045. Met by Prof Luo Diahong (Computing Manager, IRMA). Lunch and discussions with Prof Luo Diahong. Meeting at IRMA with Prof Li Jiaxi (Director of IRMA), Prof Zhang Guangdi (Se Project Manager), Prof Luo Daihong, Ms Ge Xiaoli (Geochemist) and Ms Zhang Qiling (Geochemist) to discuss work plan for the project. Dinner and discussions with Prof Li Jiaxi, Prof Zhang Guangdi, Prof Luo Diahong, Ms Ge Xiaoli, Ms Zhang Qiling and Dr Li Ji (Director of the Enshi Department of Public Health). Prepare to depart for fieldwork. Depart Beijing 0038 travel by train to Yichang accompanied by Prof Zhang and Ms Ge from IRMA. Arrive Yichang oo00. Met by Dr Su Hong Can (Director of the Enshi Institute of Epidemic Prevention) and Mr Zhang Xianying (Driver, Enshi Institute of Epidemic Prevention). Travel by mini-bus 240 km to Enshi. Arrive Enshi 1015. Met by Ms Zhang (Chief of the Office of Science and Technology, Enshi Government). Introductions to Mr Liu Zuoshen (Vice-director of Enshi Government) Mr Liu Jai Hu (Chief of the Office of Science and Technology, Enshi Government), Ms Zhang (Chief of the Office of Science and Technology, Enshi Government), Mr Liu (Vice-chief of the Office of Science and Technology, Enshi Government), Ms Hu (Member of the Office of Science and Technology, Enshi Government), Mr LA (Vice- director of the Enshi Department of Public Health), Prof Mao Da Jun (Research Fellow, Enshi Institute of Epidemic Prevention). Field programme planning meeting with Ms Zhang, Prof Mao, Dr Su, Prof Zhang and Ms Ge. Tracing of 1: 300 OM) map showing the 15 villages to be sampled during the field programme. Preparation of equipment for sampling.

4

1 2 1 1/95

13/11/95 141 1/95

15/11/95

16/11/95 am Pm

17/11/95

18/11/95

19/11/95

20/11/95 am

Pm 21/11/95 am

Pm

22/11/95 am

23/22/95 am Pm

24/11/95 am

25/11/95 26/11/95

Geochemical sampling of Luojiaba and Bajiao villages. Return to Enshi. Geochemical sampling of Shadi and Huabei villages. Return to Enshi. Geochemical sampling of Xin Tang and Yu Tang Ba villages. 1 night Shuang He. Geochemical sampling of Shatou and Fangjiaping villages. 1 night Xuan’ en. Gewhemical sampling of Xiao Gum village. Travel to Lichuan by mini-bus. Geochemical sampling of Chang Ping, Zhi Luo, Ming Shen and Nan Pu villages. Return to Lichuan. Geochemical sampling of Ji Chang and Ran Qian villages. Return to Enshi. Sorting and checking of samples. Splitting of grain samples into one sample for BGS and one for IRMA. Packing of samples for return journey to Beijing. Meeting with Ms Zhang, Mr Wang (Director of Enshi Coal Bureau), Prof Zhang and Ms Ge to discuss Se fertiliser proposals. Checking of field data and health data with Ms Ge. Meeting with Prof Mao, Dr Su, Prof Zhang and Ms Ge to discuss health statistics on Se diseases in Enshi district. Depart Enshi 1500 travel by Wuhan Airlines to Wuhan, arrive 1540. Met by Enshi local government officials in Wuhan. Meeting with Dr Zhang Hong Tai (Vice Chief Engineer, Bureau of Geology and Mineral Resources of Huabei Province), Prof Zhang and Ms Ge to discuss availability of regional geochemical samples and data for the Enshi area. Depart Wuhan 1400 travel by Wuhan Airlines to Beijing, arrive 1530. Sorting of IRMA and BGS samples and rice samples for de-husking. Rest afternoon De-husking of rice samples, translation of Enshi public health data into English. Mwting with Prof Li Jiaxi, Prof Zhang Guangdi, Prof Luo Daihong, Ms Ge Xiaoli, Ms Zhang Qiling and Mr Liu Xingping (Head of Analysis) to discuss the outcome of the field programme and future work on the project. Rest day Depart Beijing 1245 travel on flight BA0038 to LHR, arrive 1600. Depart LHR 1730 travel by hire car to Nottingham, arrive 2000.

c

5

3 . INTRODUCTION

This field visit represents the second fieldwork phase of the ODA TDR project “Prediction and Remediation of Human Selenium Imbalanw” (R6227), the objectives of which are to:

(i). Delineate risk areas in which Se toxicity or deficiency causes health disorders based on (a) mapping methodology for environmental Se levels (b) appraisal of environmental geochemical controls on the distribution of Se-responsive diseases, (c) database showing the role of Se in relation to human disease and epidemiology and (d) an integrated GIS for human risk prediction. Mitigate problems of natural Se imbalances by designing and implementing land-use planning, crop and dietary supplementation methods.

(ii).

The field programme described in this report was carried out as a collaborative exercise between the IRMA, CAGS, Beijing; Enshi District Local Government and the BGS, NERC, UK. Those participating in the field sampling programme are listed in Appendix A.

Se is a naturally occurring non-metallic trace element which is essential to human and other animal health in small doses but is harmful in excess. The range between essential levels (0.1 - 2 pg/g) and toxic levels (> 4 pg/g) is very narrow, making it necessary to carefully control the levels of intake by humans and other animals (Fergusson, 1990).

In humans, Se plays a critical role in the formation of the enzyme glutathione- peroxidase (GSH-Px) which acts as an anti-oxidant preventing tissue degeneration. In most non-industrial situations, Se intake into the body is dependent on diet and is particularly related to the Se content of food as Se concentrations in water are generally very low. Relationships between low soil and crop Se and the incidence of cardiomyopathic and osteoarthropathic disorders have been recorded in various parts of the world including China, India and Sri Lanka.

Keshan Disease (KD), an endemic, degenerative heart disease thought to be linked to Se deficiency was first described in China in 1935 where it occurs in a geographically defined belt smtching from Heilonjiang Province in the northeast of China to Yunnan province in the south-west (Figure 1). China possesses one of the best epidemiological databases in the world on Se related diseases including information on the incidence and distribution of KD and human selenosis (Se toxicity).

This database has been used in conjunction with geochemical databases to demonstratc a significant geological control on human Se exposure. However, the precise geographic areas at risk, the relationships between environmental Se and human Se intake and appropriate remediation strategies have yet to be established. Excellent links between the IRMA and the Chinese Ministry of Public Health enable a multi- disciplinary investigation involving geology, geochemistry and medial health to address these issues during the current project.

The field programme described in this report was designed by Dr J D Appleton (BGS) in collaboration with the IRMA and Enshi Local Government (Appleton, 1995) and was finalised at the start of this visit. Enshi District is one of two areas in China where Se toxicity problems have been identified in humans. In addition, KD is reported in thc north-west corner of the District which lies within the Se deficiency belt shown in Figure 1. The main objectives of the field programme were to: (i) establish the relationship between the human Se status of communities

(represented by hair samples) and their dietary Se intake (represented by grain and drinking water samples) to the local geochemical environment characterised by cultivated soils.

6

Table 2. Geological strata underlying villages sampled in Enshi District

Td, Triassic Shale and d-s mudstone. p2w permian Limestone, carbonifemus shale, calcareous

Plm permian plq penniap

mudstoae and coalstone. Limestone. siliceous rocks and marl. Limestone,quartzosesandstone.sbaleand CQahCne

CI+Z carboniferous Dolostone. limestone, dolomitic limestone and q--

D2+3 Devonian Limestone, shale and qumose sandstone

Based on translation of selected geological units from the 1: 50 OOO geology map of Enshi Disrrict

The Soil Atlas of China classifies soils in the area as yellow earths. Soils encountered during fieldwork were predominately light-brown orange silts and clays except in the north of Lichuan country where red sandy soils are derived from the Jurassic sedimentary rocks. Two soil profiles were sampled during this study, one developed on the Permian rocks of Enshi City county and the other on the Jurassic rocks of Lichuan county. Both soils consist of a narrow ( I cm) Ao horizon, with well developed A, B and C horizons (Figure 3). Soils developed on Permian rocks generally contained many shaley clasts whereas soils underlain by Jurassic sediments were relatively clast free. There was no obvious difference in organic content between the two soils. Grey gleyed clay soils were encountered in waterlogged rice paddies developed on both Permian and Jurassic rocks.

cm

1

16

66

76

Horrzon Ao

A

B

ROOI zone

C

Rock

ssdau LB

LB

LBO

Y/OR

k u l u SlCL

SlCL

SlCL

CII Rock

Shl

cm

I

16

41

I + I 81

hrboniferous base Jurassic base

Honzon Ao

A

B

C

ROOI zone

Rock

mQuK LBO

LBR

LBO

I e A u G SI

SI

SI

L B O N Si- rich

Slut

Xin Tang (HT3), Enshi City County Chang Ping (LKI), Lichuan County

Figure 3. Two idealised soil profiles from the Enshi sampling area. (Se Appndir C for explanation of abbmvi.lionr. Arrow indicate the depth of L e root mw.)

10

5 . PUBLIC HEALTH DATA

,

During the initial meeting with Enshi Local Government Officials, Prof Mao indicated that there had been no recent cases of Se toxicity reported in Enshi District. The majority of the work carried out by the Enshi Public Health Department was in the 1960’s and 1970’s following serious incidences of selenosis in humans and animals in the early 1960’s at Yu Tang Ba village, approximately 80 km east of Enshi City. This outbreak had resulted in serious hair and nail loss in the human population and in the death of livestock. It was not clear why some villages in the high Se area suffered selenosis whilst others did not. Similarly there has been no work carried out into Se deficiency disease for several years. Most studies had been carried out in the late 1960’s and 1970’s following a high incidence (up to 1%) of KD in 3-8 year old children in Lichuan county in 1969.8M of the children affected had since died. The disease still occurs in the county but the Public Health Department have no prevalence figures as they have no resources for the study of Se diseases at present. The reasons why children of the 3-8 year old age group are particularly affected are unclear. This is in contrast U) other KD areas of China wheE it is mainly women of child bearing age that suffer from the disease. Prof Mao pointed out that IDD and fluorosis are present over much of the District and the Public Health Department were currently involved in studying these two diseases. Local villagers use the coalstone for fuel and the intake of F-rich smoke from burning coalstone is thought to be the main cause of fluorosis.

.

6 . LOGISTICS OF THE FIELDWORK PROGRAMME

In order to carry out work in China a visa is required. This was arranged by Ms G Kovac of BGS via the Official Visa Department of the London Passport Office. In addition to the application form, a letter of invitation from the IRMA, two photographs and a E25 fee were required. The visa took one week to obtain and was valid for 30 days.

The quickest mode of travel between Beijing and Enshi is by air via Wuhan, however, flights between Wuhan and Enshi do not operate at the weekend. Therefore, to save time in a limited field schedule, the initial journey to Enshi was by train and then mini- bus. Three types of sleeping accommodation are available on Chinese trains: soft bunks (4 individual compartments to a carriage); semi-hard bunks (6 bunks to an open partition of a carriage) and hard bunks (6 bunks to an open partition of a carriage). The IRMA had arranged for accommodation in the semi-hard bunks as these are less expensive than the soft bunks (the fare from Beijing to Yichang was 318 yuan).Storagc space for luggage was extremely limited on the train. Yichang on the Yangste River is the nearest vain station to Enshi on the route south from Beijing. To continue the journey from Yichang to Enshi the Enshi Department of Public Health arranged a mini- bus. Enshi lies approximately 250 km south-west of Yichang and this journey took 10 hours to complete due to the tortuous nature of the roads.

The fifteen target villages were selected based on discussions with Prof Mao and Dr Su of the Public Health Department in Enshi at the start of the visit. It was agreed that where possible two villages would be sampled each day as the time schedule for thc field programme was limited. Villages were selected with this in mind and it was agreed that the field sampling team would spend nights staying in the rural areas outside Enshi City to reduce travelling time.

Ms Ge in discussion with Prof Mao pointed out that the people in the Enshi area wen: not accustomed to taking part in epidemiological studies unlike the Zhangjiakou area sampled during the first phase of fieldwork in September 1995 (Johnston, 1995). It

was agreed that the services of local hair dressers should be employed as this would help when persuading people to have their hair cut.

To facilitate transport around the a m , a mini-bus (cost approximately 500 yuan per day) and driver (Mr Uang Xianying) were provided by the Enshi Public Health Department. Prof Mao and Dr Su from the Public Health Department accompanied members from the IRMA and the BGS to form the field sampling team.

The unavailability of the 1: 50 O00 scale topographic maps and the lack of signposts in the anx made it difficult to have an awmness of distances to be travelled during the day. Straight-line distances often gave a misleading estimate of the travelling time between villages as the distance by road was invariably a lot longer. During the initial meeting with Enshi Government, Dr Su indicated that the straight-line distance between the high Se areas lying on k rmian rocks and the low Se anxs underlain by Jurassic rocks was only about 20 km. However, the distance by road between these two areas was 90 km. In the absence of accurate maps, the distances and bearings listed in Appendix B are approximations only.

The co-operation of the Enshi Local Government and the Public Health Department in particular was essential in canying out the field programme as the agreement of local community officials had to be sought prior to sampling each village. One community could be made up of one or several villages, an example of the hierarchical administrative structure for villages in the Enshi area is detailed below:

Country China Province Hubei

District Enshi County Enshi City Community Shadi

Vi I I ages Huabei and Shadi

The field programme was managed by Prof Mao, Dr Su and Prof Zhang who ensured its successful completion in a short time scale. A sampling routine was established whereby the field team would leave the accommodation at 07 15-0730, have breakfast in the mini-bus to save time and travel usually 1.5 to 2 hours to the first community. The local community director was contacted and the project explained to him. He would act as guide or provide a guide to the villages to be sampled and a local hairdresser would be found. The first village would be located and the village headman notified of the project. Prof Mao and the hair dresser would carry out the hair sampling which in some cases was time consuming as many of the villagers were reluctant to have their hair cut. The rest of the field team (including the guides in most cases) would carry out the soil, grain and water sampling. Full details of the sampling teams are provided in Appendix A. Samples were stored in the mini-bus in cardboard boxes. In order to save time, lunch was provided by local community directors before travelling on average half an hour to reach the second village of the day. Field sampling was normally completed by 17.30 and was followed by a 1.5 to 2 hours journey back to the accommodation. The samples were checked and water chemistry was carried out in the evenings following an evening meal.

The return journey from Enshi to Beijing via Wuhan involved two flights (total cost including air tax and insurance: 2180 yuan). Samples were securely packed in suitcases and cardboard boxes for the journey. Excess baggage was charged on both flights, amounting to 140 yuan from Enshi to Wuhan . The IRMA paid baggage charges between Wuhan and Beijing. Mr Liu Zuochen (Vice Director of Enshi Local Government) arranged for Enshi government transport whilst in Wuhan (cost 120 yuan). All the BGS samples were transported back to the UK at the end of the field programme and no excess baggage was charged on the international flight.

12

7, SAMPLE COLLECTION

The sample collection striategy applied in the Enshi area is similar to that employed during the first phase of lield work for the project in Zhansjiakou District (Johnston, 1995). The fifteen villages selected for the study were coded according to the following scheme: - - HT 1-5

HN 1-5 - LK 1-5 - - Low Se in the environment and KD recorded

High Se in the environment and Se toxicity recorded High Se in the environment but no Se toxicity recorded

Samples were coded EN for Enshi, numbered according to a random number list (Plant, 1973) and sample details were recorded on fieldcards. Village and sample details are summarised in Appendices B-F. Where possible, samples were collected in accordance with the recommendations of the IGCP 259 Final Report (Damley et al., 1995). Field sampling equipment is listed in Appendix G.

The main crops grown in the area art: maize-corn and rice. Crops in the mea had been harvested and grain samples were collwted from the grain stores in each village. This presented a problem in terms of the rice samples as villagers also imported rice from other areas of China which was mixed with local rice in the grain stores. Therefore, it was agreed to collect maize-corn as the main grain sample. Initially only samples of maize-corn and maize-coin-field soils were collwted. However, following the first day of sampling it was agreed that one rice paddy soil sample from each village should be collected in addition to the maize-coin soils. This would allow comparison between the soil chemistry of the waterlogged lice paddies in contrast to the dry conditions of the maize-corn fields. Where possible a local lice sample was collected to correspond to the rice paddy soil samples.

No evidence of Se toxicity or deficiency diseases were identified in populations sampled during the field programme. Three of the villagers sampled at Xin Tang (HT3) reported that they had lost hair in the past due to Se toxicity. In many of the high toxicity areas, 90% of the population were affected by fluorosis evident from the yellow and brown mottling of teeth. In Zhi Lou (LK2) the field team was introduced to a woman who had developed KD at the age of 3 in 1969 which had caused malformation of her heart. She reportcd that she was recently married and felt fit and able to work.

7.1 Soil Sampling

Sampling was carried out after the maizc-corn had bwn harvested therefore many of the fields sampled had been recently ploughed and it was not possible to distinguish A and B horizon soils. Dual crop fields were common with maize-corn often grown in the same field as tea bushes. Many of the maix-coin fields had been replanted with Chinese radish or tobacco.

7. 1. 1 Sumpling Srrutegy 5 composite soil samples were collcctcd from each village from arable land used to grow maize-corn. Where possible one composite soil sample from a rice paddy field was also collcctcd from each village. sites were selected so as to cover all the topographic aspects of arable land around the village and fields managed by diffcrent fu-mcrs. duplicate samples were collectcd from 1 in evcry 10 sample sites. near surface samples (10-30 cm; bclow A,,) were collcctcd.

3 deeper samples (35 - 45 cm), one from each Se area were collected to give an indication of variation of element concentrations with depth. 2 soil profile samples were also collected, to examine variations with depth, one from the high Se and one from the low Se area. the original strategy was to sieve the soils to - 2mm using a nylon sieve-screen in the field. Soils in the area were all d m p and often wet therefore the nylon sieve was not used due to the difficulty of cleaning the sieve-screen between samples and the problems of cross contamination a dirty sieve would cause. in order to cany out Se speciation studies at the BGS it was important that the soils retained their moistuir: content therefoir: the BGS soil samples were collected in ~

plastic securitainers.

Collection All sampling equipment (Dutch soil auger and plastic sheet) was cleaned before use. Each composite soil sample comprised 4 sub-samples collected in the same field. Using the assembled sectional soil auger, four holes were made at the corners of a square. Where possible, this square had dimensions 20 x 20 m in accordance with IGCP 250 recommendations but many of the terraced fields in the area were smaller than this and in some cases it was only possible to separate the sub-sample holes by 3-5 m. The top 10 cm organic rich layer was discarded and the deeper 10-20 cm sub- samples from the 4 holes were placed on the plastic sheet. Large stones and rootlets were removed from the sample by hand and discarded. The composite sample was homogenised by lifting the corners of the plastic sheet. The composite sample was coned and quartered to produce a split of two samples (minimum l o g ) . One split was placed in a plastic securitainer (49 x 75 mm) and the other split in a 4” by 8” KraftO paper bag. A black waterproof marker pen was used to wiilr: the sample number cmfully on the KraftB bag and on the top, side and bottom of the sauritainers (to avoid the number being rubbed off during transport). Sample containers were also coded with the letter S to indicate that they contained a soil sample. The securitainer samples were transpoi-ted back to the UK for analysis by the BGS and the KraftO bag samples remained in China for analysis by the IRMA. Duplicate soil samples were collccted in the same way from four different holes in the same field ils the original sample. Deeper soils wci’c: collected from the same four holes as the original sample. Separate samples of A, B and C horizons weft: collected from the soil profiles. Field descriptions of the soil samples are detailed in Appendix C.

Grain Sampling

Maize-corn is harvcsted uid diied on the cob in the area. The corn is dried by a combination of two methods. Firstly the cobs can bc: bunched together and hung up to dry over coalstone fires. Secondly. the cob bunches are hung up to dry in the air and the sun, this method was prevalent in the Se deliciency area where villagers have less ready access to coalstone. In both cases, the cobs are ultimately stored in thc roof space of the house which often has a slatted lloor to allow air to permeate up through the corn. In the high Se area, smoke from a coalstone lire in the main room of the house also rises up through the slattcd roof. In Yu Tang Ba (HT4) village it was possible to collect maize-corn cobs from four of the live lields sampled.

14

I

Prof Mao indicated that in addition to containing high levels of F, the smoke from the coalstone f m is also rich in Se. He suggested washing the maize-corn in deionised water prior to analysis to remove Se 'contamination* caused by the drylng process.

7.2. I Sampling Strategy 5 maize-com samples were collected from 5 different grain stores in each village where possible.

0 the grain samples were collected from villagers that fanned the fields sampled for soils.

0 in 7 of the 15 villages it was also possible to collect one locally grown rice sample corresponding to the rice paddy soil sample. a duplicate sample was collected 1 in every 10 samples

7.2.2 (9 (ii)

(iii)

(vii)

(viii)

Collection The house of the farmer that worked the field sampled for soil was located. 2-3 dried maize-corn cobs were selected from the grain store in the roof of the house. The maize-com grains were stripped off each cob by hand into a basket or sample bag. The grain was thoroughly mixed and placed in a 6 x 6 " white cloth sample bag. A black water proof marker pen was used to write the sample number clearly on the cloth bag. Local rice samples were usually found drying in their husks in baskets or on concrete slabs. One 6 x 6" cloth sample bag of rice grains was collected where possible. On completion of the field programme, enough of the maize-corn grains were removed from the cloth sample bags to fill a grey plastic securitainer (49 x 75 mm). A black water proof marker pen was used to write the sample number clearly on the top, bottom and side of the securitainers which were also labelled with the letter G to distinguish them as grain samples. The securitainer samples were transported back to the UK for analysis by the BGS and the cloth bag samples remained in China for analysis by the IRMA. On return to Beijing the husks were removed from the rice samples at the IRMA. Local villagers have rice husks removed mechanically. In the absence of a rice-dehusking machine, husks were removed at the IRMA by repeatedly beating the cloth bag of rice with a plastic hammer. The rice was then placed in a tray and taken outside to be shaken in the wind allowing the husks to be winnowed off. Ideally for this process the tray should be made of plastic, however, only metal (Zn galvanised steel ) trays were available at the IRMA. Once de-husked, the rice samples were split 5050 between grey plastic (49 x 75 mm) securitainers and 8 x 13 cm paper sample bags. The securitainer samples were numbered and coded G to identify them as rice grain samples and were transported back to the UKIor analysis by the BGS. The paper bag samples remained in China for analysis by the IRMA.

7.3 Water Sampling

Unlike the Zhangjiakou area sampled during the first phase of fieldwork (Johnston, 1995), villages in the Enshi area were not served by drinking water wells. All villages were supplied by spring water. In most cases a small lm x lm reservoir pond had been constructed to trap the spring water. In each village the main spring in the village was sampled. In Xin Tang (HT3). Shatou (HT5), Fangjiaping (HN3) and Xiao Guan (HN4), the villages covered large areas and it is likely that they contained more than one spring but due to the time constrains on sampling it was only possible to sample the

15

main spring. Zhi Luo (LK2) and Nan Pu (LK4) both contained two springs but in each case only one was suitable for sampling. In the villages of Shadi (HT1) and Huabei (HT2), the population had been advised not LO drink the spring water due to the high Se content. In Shadi the villagers had been instructed to take water from another spring in an adjacent watershed. However, due to the distance of this alternative water source, villagers still occasionally used water from the Se-rich spring. In Huabei, the village had been supplied with a piped water supply from elsewhere and only used water from the Se-rich spring very rarely. In both cases, however, the Se-rich springs were sampled so that Se in the local hydrogeochemical environment could be determined.

7.3, I Sampling Strategy water samples were collected from the main or only spring in each of the 15 villages sampled close to the areas where the soil and grain samples had been collected. duplicate samples were collected 1 in every 5 samples.

Collection At each site, the following suite of water samples were collected: - Three 30 ml filtered water samples collected in trace element free

- One 100 ml filtered water sample collected by the IRMA in plastic bottles

- One 30 ml unfiltered water sample collected in a polystyrene SteralinO vial for

- One 250 ml unfiltered water sample collected in a polyethylene bottle for

A waterproof black marker pen was used to write the sample number clearly on the sides of the bottles. Numbers were also written on the lids and bottom of the 30 ml NalgeneB bottles to avoid the numbers being rubbed off during transport. The 30 ml NalgeneO bottles were labelled to indicate which samples would be acidified as follows:

polyethylene NalgeneO bottles.

supplied by them.

pH and Eh determinations.

bicarbonate and conductivity dekiminations.

UA= unaciditied HA = acidified with hydrochloric acid NA = acidilied with nitric acid

Each filtered water sample was collected using a 25 ml plastic syringe and a SwinnexO filter cartridge pre-loaded with a 0.45pm MilliporeB cellulose filter. A new filter cartridge was used for each site to avoid any possible cross- contamination between sites. At each site the liltered wakr samples were c o l l a k d first avoiding disturbance to sediment in the bottom of the spring-fed water reservoir. Water was drawn into the syiinge which was rinsed out twice. The syringe was filled with water again and connected to the filter cai-tridge which was also rinsed out twice. The syiinge was refilled and the sample bottle was rinsed out twice with filtered water piior to being filled. The 30 ml Nalgenem bottles were filled to the shoulder. Both the 30 ml SteralinO vial and the 250 ml polyethylene bottle were rinsed out twice in the water reservoir. Where possible, the vial and the bottle were both submerged underwater whilst the caps were secured making sure that no air was trapped in the sample container. This minimises the degassing of HCO, in the samples. Care was taken to kwp all bottles and lilkrs clean and uncontaminated by human touch. 30 ml samples collected for trace clement analysis at the BGS were acidified within 4 hours of the end of fieldwork each day. NA and HA samples were acidified by the addition of 0.3 in1 (8 drops) ARISTAR grade nitric and hydrochloric acid respectively. Addition of 1% v o h o l acid reduces the pH of the samples to approximakly 1 .U, thus preventing adsorption of dissolved

16

metals to the interior walls of tlie storrrge bottle and minimising post-sampling microbial activity. Care was taken to avoid introducing contamination through the plastic dropping pipettes, each of which were stored in a plastic self-seal bag and did not come into contact with bench surfaces. Eh and pH measurements, bicarbonate and conductivity determinations were also carried out at the end of each day's sampling. Procedures iire detailed in Appendix H and results are listed in Appendix E. Following the measurements, these samples were discarded and the sampling containers reused. Two field-blank UA, HA and NA samples were made up near the start and end of fieldwork. 30 ml NalgeneO bottles were rinsed twice with filtered deionised water, filled to the shoulder with filteicd deionised water and acidified in the same way as the samples. The field-blanks were numbered in the same way as the samples according to the random list. AT ALL STAGES GREAT CARE WAS TAKEN TO ENSURE THAT SAMPLE BOITLE TOPS WERE SECURELY TIGHTENED. The UA, HA and NA water samples were transported back to the UK for analysis by the BGS and the 100 ml liltcrcd water samples remained in China for analysis by the IRMA.

Hair Sampling

Hair samples were collected from inhabitants of the 15 villages to represent the Se status of the local population. In many cases it was dif!icult to persuade people to have their hair cut. Women in paizicu1a.r were very reluctant to lake part in the study and only two women were sampling duiing the programme. Following the serious Se toxicity problems at Yu Tang Ba (HT4) in the early 1960's the government had moved the population off the land. One family of three prsons have moved back to the area in the last two years therefore i t was only possible to obtain three hair samples at this village. In the village of Xiao Guan (HN4). i t was only possible to persuade three people to take part in the study. A fourth potential candidate was found but his hair was too short to sample. In the KD area in the north of Lichuan County, i t is mainly children that suffer from the disease therefore hair from children was sampled. It was not possible to collect duplicate hair samples.

7.4. I Sampling Strutegy hair samples were collwted from 5 individuals in each village where possible, individuals from different I'amilies were selected where possible, individuals from lams where soils and grain samples had been collected were sampled individuals of a range of ages were sampled during the study, unfortunately it was not possible to include a reasonable mix of male and female subjects in the study for the reasons described above age, health, disease and medication details were recorded for each individual

7.4.2 Collection (i)

(ii)

(iii)

With the assistance of the local guides and village headman, Prof Mao identificd individuals to be sampled. Samples were collected using scissors cutting hair at the nape of the neck and lower head as Se tends to conceiitrw in human hair in this part of the head. Approximately 10 g of sample was collected and placed in a small plastic self- seal bag. The bag was numkrcd in a similar way to the soil and grain samples using a waterproof black marker pn.

17

(iv)

(v)

A questionnaire (in Chinese) was completed for each individual sampled. A translation of the results of these questionnaires is given in Appendix F. On return to Beijing, the hair samples were split 50:50 to provide a complete set of samples for both the IRMA and the BGS. Hair in the original sample bags was transported back to the UK for analysis at the BGS.

7 . 5 Other Samples

7.5. I Tobacco Following the Se toxicity problems at Yu Tang Ba (HT4) in the early 1960's the local government no longer allow the local population to eat any of the grain grown there. All food crops grown in the Se-toxic a m are exported. However, grain samples from the village were still collected for this study to give an indication of their Se content. Tobacco is grown at the village mainly for export, however, the population do also smoke the tobacco they produce. A sample of tobacco leaves was therefore collected from the village. Dried tobacco leaves were collected and placed in a white cloth sample bag and then split 5050 to provide samples for both the IRMA and BGS. The BGS sample was transported back to the UK for analysis in a grey plastic (49 x 75) mm securitainer coded with the letter T to indicate a tobacco sample.

7.5.2 Pig Huir Although no Se toxicity affects were reported in humans in the area sampled, at Xing Tang (HT3) and Shatou (HT5) hair loss was found in pigs suffering from Se toxicity. A sample of hair from the pig in Xing Tang village was collected in a small plastic self- seal bag. The sample was l a w split 50:50 to provide one sample for the IRMA and one for the BGS.

8 . SUMMARY OF MEETINGS

8.1 Initial meeting with the IRMA on 9/11/95

Participants: Prof Li Jiaxi IRMA Prof Zhang Guangdi "

Prof Luo Diahong Ms Ge Xiaoli Ms Zhang Qiling Ms Fiona Fordyce BGS

L'

6'

"

Drift versions of reports on the planning visit to China camied out by Dr J D Appleton (BGS) in July 1995 and of the first phase of fieldwork cai-ried out by Dr C C Johnston (BGS) in September 1995 were presented to the IRMA. The IRMA was asked to study the reports and so that their comments could be relayed back to the BGS by Ms Fordyce for inclusion in the final vcrsions ofthe visit repoiz~.

Initial results from the BGS for total Se concentration in the waters sampled during the first phase of fieldwork in Zhangjiakou Diskict were prwnted and discussed. Zhangjiakou District is an area of Se deficiency and KD incidence. Three mas had been studied duriyg the k l d programme as follows:

NK - low environmental Se a i d no KD incidence MK - low environmental Se and moderate KD incidence HK - low environmental Sc and high KD incidcncc

Drinking waters sampled in the area all came from wells with the exccption of one village which was served by a rcscrvoir. A sircam had been sampled in one village in

18

addition to the well. There were no obvious diffetences in total Se between the reservoir and stream samples and the wells. To make comparisons between data, the reservoir sample and the stream sample had been excluded from the dataset and the duplicate samples had been averaged. Plots of total Se concentration against field measurements (pH, Eh, bicarbonate, conductivity and sample temperature) for 14 well samples were discussed. One sample (duplicate ZI 16/32), contained markedly higher amounts (1.16 pg/l) of total Se than the other samples and did not fit the trends seen in the other data The sample was taken from the deepest well in the area but m n s for the high total Se content required further investigation. With the exception of this sample, the total Se content in water appeared to increase as the bicarbonate concentration of the water increased.

Peatson correlation coefficients calculated for the dataset showed that there were no significant correlations (95% level) between total Se concentration in the water and other parameters largely as a result of the one outlying sample. Significant (99%) correlations between bicarbonate concentration and pH and between bicarbonate concentration and conductivity were recorded as would be expected. Bicarbonate concentration, pH and, with the exception of the outlying sample, total Se concentration all decreased from the low KD area to the high KD area.

Further interpretation of these results will be carried out once further analytical data is available for the waters and for the other sample types also. The IRMA will compare the results of the BGS analysis to the results of their analysis of the same samples.

The results for a Se-rich mineral water sample collected from the LAO Huo Dong water- bottling plant in Enshi by Dr J D Appleton during his visit were also discussed. The mineral water is reported to contain 16 pg/l Se. The BGS sample had been collected directly from the spring feeding the commercial bottling plant and analysis at the BGS had shown it to contain only 4 pg/l total Se. The IRMA would check this result against their analysis of the same sample. It was possible that some of the Se may have been adsorbed onto the walls of the sample container as the sample had not been acidified after collection. The BGS would conduct further acid leach experiments to ascertain how much Se was adsorbed on the container walls.

The logistics and rationale of the current field programme were discussed and discussions continued over dinner in the presence of Dr Li Ji, Director of the Enshi Public Health Department.

8.2 Initial Meeting with Enshi Local Government OMicials 11/11/95

Participants: Ms Zhang Enshi Office of Science and Technology Prof Mao Da Jun Dr Su Hong Can Prof Zhang Guangdi IRMA MsGe Xiaoli Ms Fiona Fordyce BGS

Enshi Institute of Epidemic Prevention bb

‘6

As detailed in previous sections of this report, the rationale and the logistics of the field programme were discussed. The fifteen target villages were selected and a field programme schedule devised. Previous epidemiological and geological studies carried out in the area were also discussed. The 1: 300 0oO Enshi District map was traced to show the location of the fifteen villages.

19

8 .3

Participants: Mr Wang Director, Enshi Coal Bureau Ms Zhang Prof Zhang Guangdi IRMA Ms Ge Xiaoli Ms Fiona Fordyce BGS

Meeting with Enshi Coal Bureau to discuss the Se fertiliser project 2011 1/95.

Enshi Science and Technology Office bb

The local government in Enshi considers it a priority to utilise the high Se in the area to produce Se enriched products designed to alleviate the Se deficiency problems in other parts of China. Products include Se-rich tea, tobacco, grain, vegetables and mineral water. In addition, a &rich fertiliser and animal feed additive have been produced. Enshi Local Government and the IRMA propose that trials of the fertiliser product should be conducted in the areas of Se deficiency under investigation in the cumnt project. These trials would form part of the investigations into methods of alleviating Se deficiency. Dr J D Appleton (BGS) had some discussions with Enshi Government regarding the Se fertiliser during his visit in July, further discussions to provide more information on the Se fertiliser were held during the present visit.

The development of Se resources in the Enshi area is the responsibility of the Science and Technology Office under the direction of Mr Lui Jai Hu. The Enshi Coal Bureau, the Bureau of Preventative Medicine and the Chinese Academy of Agriculture in Enshi have a l l been involved in developing and testing the Se fertiliser in conjunction with the Office of Science and Technology. Tests and development have been carried out over the last 5 years. The Coal Bureau has developed the method to produce the fertiliser for use in trials but does not have the money to set up a factory for production on a commercial scale. The Enshi Government are cumntly holding discussions with the government of Hubei Province with regard to funding for Se resource development.

The Se-rich fertiliser and animal feed products are derived from the Se-rich coalstones of the area. To date, two types of animal feed product have been produced. The initial product consisted of crushed coalstone which was added directly to animal feed. This product has been tested in Sichuan Province by the Sichuan Geological Survey and in Heilingjai Province. In both areas the coalstone was added to cattle feed and chicken feed resulting in an increase in production and Se content of milk and eggs. The current animal feed additive is produced by the same process as the fertiliser. Trials have concentrated on using the product as a fertiliser rather than animal feed.

The Se-rich Enshi fertiliser (Se-40) is a mixture of Se-rich trace element fertiliser derived from the coalstone and local NKP fertiliser. The fertiliser typically contains > 40 mgkg Se and 6-25 % N, K,O and P205 (Table 3). Se-rich coalstone is wetted with a special solvent patented in China to produce the Se-rich trace element fertiliser. This product is also rich in other trace elements including Fe, MO, V, B, Mn, Hg, As, Cd, Ni, Cu and Zn (Table 3). The exact method of production of the Se-rich (Se-40) fertiliser is confidential but Na selenite is not used in the process.

Two types of trials have been camed out jointly by the Coal Bureau and the Institute of Agricultural Science on the Se-40 fertiliser in the Enshi area over the past 5 years:

(i). Provide local farmers with 3 kinds of fertiliser: Se-40 fertiliser; local NKP fertiliser and NKP fertiliser imported from the Philippines to compare crop yields using the different fertilisers.

(ii). Provide the Agricultural Institute in Enshi with the same 3 fertilisers for trials on larger fields noting differences in yield and Se content of crops.

20

Results were monitored every year on a variety of crops including rice, maize- corn, vegetables, tea and tobacco. The tests were carried out in all parts of Enshi district, in Se deficient, normal and toxic areas. Addition of the S e 4 fertiliser resulted in a 5 - 15% i n c m in yield of all crops in all areas compared to the local N?W fertiliser. The increase in yield was more marked in the Se deficient than the Se toxic areas. The Se content of crops also increased in all cases. Results of this work have been recorded in a confidential report not available to the IRMA or the BGS.

Analysis of the S e 4 fertiliser used in the trials has been carried out by an authoritative professional laboratory of the National Geological Team in Enshi on behalf of the Cod Bureau (Table 3). The exact methods of analysis (extractions used etc.) were not detailed in the analytical report.

Table 3. Results of chemical analysis of the Enshi Se fertiliser.

Am B Ca Cd aU PeK,O MO Mn N Ni I% P,O, Se si U V Za

Total Wt % 2.35 4.14 1.43 15.52 T d m g / k g 9 48 30.8 272 25 425 181 2360 105.8 25 149.7 19.2 Extractablc Wt % 0.23 4.35 0.22 Extractable rn@g 12.4 44.5 I I 144.7 7.1 439 6.7

The Coal Bureau and the IRMA did not appear to have canied out a cost benefit study for the production of the Se-40 fertiliser. They did, however, report that there are no other sources of Se fertiliser in China and it is not produced industrially. The Coal Bureau and a metal factory were involved in a pilot project to extract Se from the coalstone several years ago but this prqject was not economically successful. The Se-40 fertiliser costs -1.5 yuan per kg to produce. Prior to the visit, the BGS had ascertained a world market price of 100 yuan for 1 kg of 99% pure Se. Mr Wang was surprised by this price as Na$O,costs 300 yuan per kg in China. It w u calculated that 1 kg of the N%SO, available in China would contain 420 g Se. One kg of the Se-40 fertiliser contains 0.15 g Se but also contains the other trace elements. Trace element fertilisers cost 3 yuan per kg in China.

Prof Zhang advised the BGS that in order to test the Se-40 fertiliser, 30 kg/ mu had been applied to fields (15 mu = 1 hectare). Manufacturing 30 kg of the Se-40 fertiliser requires 10 kg of the Se-rich trace element fertiliser and 20 kg of the local NKP fertiliser (cost of Se-40 = - 1.5 yuan per kg). To make a fertiliser with the equivalent concentration of 40 mgkg Se from Na$O,, 30 g N%SO,and 30 kg local NKP fertiliser would be required. If the cost of 1 kg N%SO, is 300 yuan and the NKP local fertiliser costs 1.2 yuan/kg then the Se-40 fertiliser costs 39 yuan per 30 kg whereas the N%SO, fertiliser costs 46 yuan per 30 kg to produce.

It is proposed that the fertiliser should be tested in Se deficient area of Lichuan in Enshi District in the first instance with further trials in the Se deficient study areas in Zhangjiakou, Chixian and Shexian, north-central China It was estimated that it would cost 400 yuan to transport 1 tonne of the fertiliser to Zhangjiakou, the area furthest north of Enshi.

Prof Zhang reportcd that then: was a large potential market for the Se trace element fertiliser in China. N, K and P fertilixrs were widely used but farmers were only now becoming aware of the importance of trace element fertilisers and were keen to start using them. A Department of Trace Element Fertiliser Studies has recently been set up at Beijing University. Prof Zhang stressed the importance of this project to demonstrate the benefits of Se trace element fertiliser in various regions of China and to publicise the importance of Se fertilisers to agriculturists, government and farmers.

21

Ms Zhang asked if there was any information on the application of Se fertilisers in the UK. She had read that in Finland Se was added to crop irrigation water rather than applied in fertiliser form. The BGS will provide the lRMA and Enshi Government with information on methods of Se fertiliser application outwith China at the earliest opportunity.

8.4

Participants:

Meeting with Enshi Public Health Department 21/11/95

Prof Mao Da Jun Dr Su Hong Can Prof Zhang Guangdi IRMA Ms Ge Xiaoli Ms Fiona Fordyce BGS

Enshi Institute of Epidemic Prevention bb

bb

During Dr J D Appleton’s (BGS) planning visit to Enshi in July 1995, Prof Mao and Dr Su had given the IRMA a copy of a report detailing the results of investigations carried out into Se toxicity problems in the Enshi area. The IRMA had originally agreed to provide the BGS with an English translation of this report. Prof Zhang indicated that due to the very limited staff-time available on the project, the IRMA would not be able to provide a translation.

Prof Mao and Dr Su supplied the IRMA and the BGS with copies of a paper that Prof Mao had written on the features of KD in the area (Mao, et al. 1987) and an untitled report of investigations into Se toxicity. The results of these two studies were discussed and translations of the figures in these documents were provided by Ms Ge on return to the IRMA.

The paper on KD was based on data collected between 1969 and 1983. Following a serious outbreak of KD in Lichuan county in 1969, the number of cases of the disease in villages in the north-west of the county was recorded over a 14 year period. Details of the incidence rates are summarised in Table 4 and Figures 4 - 7. Total Se was determined in a small number of water, rice and hair samples in the area.

22

1969-1 983 Average Number of I)rsuce R a ~ e Number of 'k of

Duchr v I Ilage - Dub - I / 1oOOopq -_- P d J I i O O KD C u u

Clung hng 2031iY r 5 9 Muo D.q 24911 3 1 Tong LuoGuaa 1 2 8 5 1 3 1 J1.o 2hu XI i s 4 9 7 5 Jim NUI 24679 3 LeFuDila 22868 3

l ( J : . O f j

6 . 2 0 io.as

2 . 3 0 0.87 d.94

117 4 5 . 2 19 9 U . S 18 85.7

1 80.0 .J 100.0 2 C C . 7

I

,

Totd 1?1428 3 12 18.30 1 6 3 5 2 . 2

Table 4. KD incidence in selected villages in Lichuan County 1969 - 1983.

Figure 4. Distribution of KD disease in the 14 village areas of Chang Ping community, Lichuan County.

23

Number of KD cases

I 0 0

80

LO

40

20

L 196% 1516 im

Y W

Figure 5. Number of KD cases in each year, 1969 - 1983 in Lichuan County.

NlUnba of KD cases

Month

Figure 6. Percentage of KD cases occurring in each month of the year in Lichuan County.

1 = % of KI) cases who died in year 1 2 = Ok, of KD cases who died in year 2 3 = 96 of KD cases who died in years 3-1 1

Figure 7. Percentage KD cases who died over an 11 year period in 1 Lichuan County.

24

, The Enshi Public Heath Department are no longer monitoring Se deficiency in the area but they do monitor heart rates of the population to check for heart abnormalities.

Work from studies into Se toxicity in the area involved sampling several of the high Se villages in the afea (Figure 8). The report of these studies presented by Prof Mao and Dr Su mainly consisted of figures showing i~su l t s from geological, soil, human and animal health investigations. The itxults are summarised in Figures 9 to 2 1.

Figure 8. Villages sampled in the Enshi Public Health Department Se toxicity investigation.

25

Prof Mao also supplied photographs showing the eCTwts of Se toxicity on human hair and nails taken during die 1963 Se toxicity incident in die area.

Dr Su reported that GSH-Px activity in the population of the high Se area was no different to areas of ‘noimd’ environmental Se. However, GSH-Px activity in the low Se area was below normal. Average intake of Se in the Se-rich area was 550 pgkg per day in contrast to a daily inIllkc of 400 pdkg in the low Se area. Se toxicity and deficiency diseases were not evident in either area and the Public Health Department suspect that this is due to die intervention of other elements such as As, Pb and Cr preventing the developmcnt of d i x w .

Ms Fordyce asked how the results of the present study should be reported to the Enshi Public Health Department. I t was agreed that the BGS should report results to the IRMA in the first instance and the IRMA would inform the Enshi Health Department.

Figure 9. Se content of various coniponents of the Enshi coalstone.

26

Enshi

Xuan ‘en Jianshi Heqeng

t 6

Lichuan 9 4

Xianfeng r t

Badong Leifeng

Se content of coalstone mgkg

Figure 10. Se content of coalstone in various counties in Enshi District.

Se p g h 3 in air

5 6 7 hours

Figure 11. Se content of air through time during the burning of a coalstone fire.

27

Figure 12. Se concentration i n soil before and during the burning of a coalstone fire.

Figure 13. Se content with depth of a soil profile.

28

1 Shadi 4 Chun Mu Ying

2 ShuangHe 5 Mu Fu

3 XinTang 6 Nun Tan

Figure 14. Distribution of Se toxicity i n various villages.

20

Figure 15. Number of cases of Se toxicity by year.

30

I

100 ' I

t ! \ I

i Numberof ' 50 Se toxicity i

I cases

I i ( I \

Year

Figure 16. Number of cases of' Se toxicity 1923 - 1983.

t

. i - . . .

.. . I 1

! - . I

- - . . .

Figure 18. Symptoms of Se toxicity in a statistically sampled population of 180 from Se toxicity villages in Enshi District.

Se mgkg

23

\ 6

'

Liver Kidney Brain Womb Intestine Stomacb Skin Muscle

Figure 19. Se concentration in various organs and tissues of a pig.

32

0.1

0.0 I - Water soil Corn Hair Coalstone

Figure 20. Se concentration in various sample types from Yu Tang Ba village in 1981.

2 E 6) cn

soil

3 I 968

Figure 21. Se concentration in corn and soil at Yu Tang Ba village in 1963 and 1988.

33

8.5 Meeting with the Bureau of Geology and Mineral Resources of Hubei Province 22/11/95.

Participants: Dr Zhang Hong Tai

Prof Zhang Guangdi IRMA Ms Ge Xiaoli IRMA Ms Fiona Fordyce BGS

Vice Chief Engineer, Hubei Bureau of Geology and Mineral Resources

During the initial stages of the current project, it was anticipated that regional geochemical data (1: 200000 scale) available for all of China would be incorporated inb a GIS system and related to the public health data. Although the geochemical maps of China have been published, the raw datasets and sample archives are confidential and are unlikely to be made available to the project. The IRMA are in the process of requesting access to regional geochemical data reievant to the specific areas of detailed study during the project and arranged a meeting with the Hubei Bureau of Geology and Mineral Resources to discuss the possibility of obtaining the regional geochemical data for Enshi District. Prior to the meeting Ms Fordyce suggested that the local geological bureau in each of the areas of detailed study should perhaps be included in the project to ensure that the data were made available. The IRMA was reluctant to accept this proposal as they have no money to pay for the involvement of the geological bureaux in the project. Ms Fordyce was unaware of the financial position of the project but suggested there may be a possibility of the BGS providing project funds to include the geological bureaux. Alternatively Ms Fordyce suggested that the project may be able to buy the regional geochemical data The BGS national geochemical dataset is also confidential but raw data can be purchased for a fee.

During the meeting, Dr Zhang indicated that Enshi District had been mapped on a regional scale as part of the national geochemical mapping grogramme. Sueam sediment sampl.;s were collected at a density of 1 per 1 km and 4 adjacent samples were composited to give a final sample density of 1 per 4 km2. Multi-element analyses, including results for F, were available for the samples, but the list of determinands did not include Se or S. The raw data and sample archive were confidential and were managed jointly by the Bureau of Geology and Mineral Resources and the Institute of Geochemistry. Dr Zhang appreciated the importance of the raw data to the project and the need to reanalyse archive samples for Se in particular. Dr Bang explained that the amount of sample retained in the archives was limited and that it may only be possible for the project to access samples on the basis of 1 per 9 km2. Although Dr Zhang agreed in principal to release the data, he first had to discuss the matter with the Institute of Geochemistry and would contact the IRMA to inform them of the outcome.

8.6 Concluding meeting with the IRMA 24/11/95

Participants: Prof Li Jiaxi IRMA Prof Zhang Guangdi "

Prof Luo Daihong Mr Liu Xingping Ms Ge Xiaoli Ms Zhang Qiling Ms Fiona Fordyce BGS

' b

b b

b b

b b

Ms Fordyce reported that the Enshi field work had been successfully completed within 6 days and thanked the IRMA for the excellent arrangements they had made.

Fifteen villages were sampled: 5 with high environmental Se and Se toxicity problems, 5 with high environmental Se and no toxicity problems and 5 with low environmental Se and KD incidence.

34

In total 562 samples had k e n collcclcd us follows:

. . IRMA

83 maize-corn soils 10 rice paddy soils 3 deeper maize-corn soils 5 soils from 2 soil profiles (8 maize-corn soil duplicates)

82 maizecorn samples

'IS111 1' -

7 rice samples

18 w- camp (8 maize-corn duplicates) . . IisinG 18 filtered waters

. . (3 water duplicate samples)

71 human hair 1 pig hair

compisinL -

101 soil B G S

83 maize-con1 soils 10 ricc paddy soils 3 deeper maize-corn soils 5 soils from 2 soil profiles (8 maize-corn soil duplicates)

82 inaizecom samples 7 rice samples

20 wJtcrsampies c- (8 maize-mm duplicates)

18 liltered waters 2 blank waters (3 water duplicak samples)

7 1 Iiuman hair 1 pig hair 1 t o b a c m

. . . ..

. . . >

. . 72 hair Sam ]es

The IRMA would carry out multi-clement analysis on 20 - 30 % of the samples using a variety of techniques including ICP-MS uid polography. Se would be determined by MFS.

The BGS samples would be analysed by AFS for total Se (and loss on ignition (LOI) in soils) in the first instance and decisions on further analysis would tx based on these initial results.

The problem of possible Sc contamination due to the drying of the maize-corn samples over coalstone fires was discussed. The IRMA agrwd with Prof Mao's suggestion that the maize-corn samples should be washed in dcionised water to remove the contamination thus allowing accur;~tc comparisons of the Se content of the grain with that in the environment (soils). Ms Fordyce pointed out that the local villagers did not wash the g r i n prior to milling and consumption therefore the dietary intake of Se from maize-corn would include the coalstone smoke component. If comparisons were to be drawn between the hair sample results and the g r i n results, the grain samples should not be washed. It was agrced h a t the pl.cpxLttion of the grain samples should be discussed further with the uialysts at the lRMA and the BGS.

Ms Fordyce rcportcd h a t no symptoms of Se toxicity or deficiency diseases had been recorded in any of the local population during sampling.

The meeting between the IRMA, the BGS and the Enshi Coal Buixau was discussed. Prof Li was kwn to know the results of the Se fertiliser trials. Ms Fordyce related the information that had been providcd by the Enshi Cod Bureau but indicatcd that the report detailing the results was conlidential and was not available to the IRMA or the BGS.

Prof Li was interested in any inl'ormalion about Se fertilisers in the UK. Ms Fordyce explained that the Enshi Government wcre also interested in information about Se fertilisers outwith China. Dr J D Applcton (BGS) had good contacts with agricultural and veterinary scientists and would provide the IRMA with information on Se fertilizers as soon as possible.

The proposed Enshi Se fertiliwr trials were discussed. The IRMA m very keen that experiments involving the application of the Enshi Se fertiliser to the areas of Se deficiency studied in the project should begin as soon as possible and should form a major part of the remediation programme of the projcct.

Prof Li suggested that a commercial Se fertiliser manufactured outwilh China should be tested along with the Enshi Se fertiliser in crop tiials and that the build-up of Se in the environment following several years of application should be monitored. Ms Fordyce agreed that these would be interesting experiments and would relay these suggestions to Dr Appleton.

The total budget of the Se fertiliser trials was estimated to be 200 OOO yuan of which the Enshi Government had agreed to pay 20%, the IRMA 30% and it was hoped the BGS would provide 50% (f7700). The IRMA hoped to instruct Enshi Local Government to begin the trials in the low Se ai-ea of Lichuan county in December 1995 but they could not go ahead until they had confoimation of the BGS funding. Ms Fordyce explained that she could not comment on the project funding but would report the discussions with the Enshi Coal Bureau to Dr J D Appleton who would consult agricultural scientists and the ODA with regard to the project. Ms Fordyce again stressed the importance of the economic viability of the Enshi fertiliser and that this may have to be investigated further before the project could go ahead.

Ms Fordyce reported that Prof Mao and Dr Su had provided the IRMA and the BGS with reports of two studies into Se toxicity and Se deficiency in the Enshi area. It was still unclear, however, what epidemiological data would be available to the project as no work into Se diseases was cun.ently canicd out in the Enshi area.

Dr J D Appleton and Dr C C Jolinston’s visit rcporw were discussed. The IRMA were concerned that Dr C C Johiiston’s report indicated that diey were to carry out multi- element analysis for all thc: Zhangjiakou samples. Due to funding restrictions, IRMA would only analyse 20-309) of the Zhangjiakou samples. IRMA weiv also concerned that there was no mention of the analysis to be caiiicd out by BGS in the report. Ms Fordyce agreed that the section in the report detailing the analysis of the samples needed clarification.

Dr Liu Xingping expressed concern that Dr J D Appleton’s report seemed to suggest that the LOI results for soils would give an indication of total organic-Se content. Ms Fordyce clarified the situation explaining that results for LOI gave an indication of the total organic content of the soils and would ensure that this was made clear in the report.

Referring to Dr J D Appleton’s report, Dr Liu Xingping was keen to know what methods of Se speciation analysis the BGS had developed. Ms Fordyce explained that the BGS was in the process of developing methods of Se speciation in conjunction with a student at Reading University in the UK. Mclhods would be based on AFS analysis. As with Dr C C Johnston’s report, the section on analysis in Dr J D Appleton’s report required clarification.

With the exception of these minor points, thc IRMA were satisfied with both visit reports.

Dr Liu Xingping indicatcd h a t the IRMA arc hoping to develop new methods of organic-Se species determination bascd on HPLC methods but that the sample preparation techniques are very complicated. He wished to know if the BGS had plans to determine organic-Se species.

Prof Li asked which international standards the BGS used in analysis as the IRMA were keen to carry out inter-laboratory tests twtwccn the IRMA and the BGS using the

36

I

Same international standards. Ms Fordyce explained that the BGS had a suite of international soil standards and a rye gruss and cabbage standard for vegetation analysis. Analysis of hair samples for the Se project would be a new venture for the BGS and she was not certain of the details of international hair standards. Ms Fordyce agreed that the IRMA and h e BGS should llnalyse the same international standards during the project so that the ~xsults for the two sets of samples could be compared. Ms Fordyce would provide the IRMA with a list of the BGS international standards and reference material could be supplied to them during the next visit of BGS personnel to China.

Prof Li expressed great interest in future collaborative projects between the BGS and the IRMA. Other possible areas of ivsearch into geochemistry and health included IDD and fluorosis. Prof Li stakd that much work was canied out already in China on IDD and fluorosis might prove a moiv original topic of study. Ms Fordyce would report the interest in IDD projects to Dr C C Johnston who specialised in iodine geochemistry at the BGS and would discuss the possibility of projects investigating fluorosis with Dr J D Appleton.

In Summary the main poinb of the mccting were:

1. 2. 3. 4. 5 . 6.

Decision on BGS funding for the Se fertiliser trials Provision of information on Se fcrtiliscrs outwith China Clarification of analytical methods in reports Provision of infoimation and matciial for inkmational analytical standards Decision on a method for preparing Enshi m i x - c o r n samples for analysis Future projects ktwcen the IRMA and the BGS

9 . REFERENCES

Appleton J D. 1995. Report 011 Planning Visit to China 12-27 July 1995. British Geological Survey Overseas Geology Series Twhnical Report WC/95/76/R.

Crounce R G, Pories W J, Bray J T and Mauger R L. J 1983. Geochemistry and man: health and disease. 1. Essential clcmcnts. In: Applied Environmental Geochemistry. Thornton, I. (ed). Academic Press, London.

Fergusson J E. 1990. Thc Hcavy Elcincnls: Chemistry, Environmcntal Impact and Health. Pergamon Press, Oxford.

Johnston C J. 1995. Field Visit to the Zhang.jiakou District, Hebei Province, China 6- 24 September 1995. British Geological Survey Technical Report WC/95/77/R.

Mao D J, Gong X G, and Liu J Y. 1987. The features of kcshan disease in Lichuan County, Hubei Province. Environmcntal Scicncc Publication of China. No. 76. pp 76- 78.

Plant, J A. 1973. A rJndoin numbcring sysicm for gcochcmical samplcs. Transactions of the Institute of Mining and Mctallurgy. B82. pp 63-66.

Times Atlas of the World. 1992. Comprclicnsivc 9th Edition.

Zheng B S, Hong Y T. Zhao W, Zhou H Y, Xia W P, Su H C , Mao D J, Yan L R and Thornton I. 1992. The Se-rich carbonaccous siliceous rock and endemic selenosis in south-west Hubei, China. Cliincsc Scicnce Bulletin. Vol 37. No. 20. pp 1725- 1729.

37

10. ACKNOWLEDGEMENTS

The author extends grateful thanks for all the excellent assistance and hospitality provided by the field party (listed in Appendix A). Prof Mao, Dr Su and Prof Zhang are thanked for ensuring that ihe fieldwork was successfully completed in a very short time scale. Sincere thanks are extended to Ms Ge who, in addition to being a highly efficient gemhemist and water chemist, tirelessly acted as interpreter and guide to Chinese food and customs ensuring a veiy enjoyable visit. Mr Zhang must be thanked for his excellent driving on tortuous roads. The exceptional co-operation and hospitality of Prof Li, and all the staff at the IRMA, particulru.ly Prof Luo and Ms Zhang, are very gratefully acknowledged. Dr Li and all members of the Public Heath Department and Enshi Local Government at district, county and community level (listed in Appendix A) are thanked for the excellent imangements they made and their enthusiastic participation in the project.

APPENDIX A. DETAILS OF THE FIELD SAMPLING TEAM

Prof Zhang Guangdi, Project Managcr

Ms Ge Xiaoli, Geochemist

Prof Mao Da Jun, Research Fellow

Dr Su Hong Can, Director Mr Zhang Xianying, Diivcr

Ms Fiona Fordyce, Gcochcm is1

of 1.- . . ..

Guide: Soil sampling: Grain sampling: Water sampling: Hair sampling:

Arrangements: Guide: Soil sampling: Grain sampling: - - Water sampling: Hair sampling:

of Shad1 Arrangements:

Guides: Soil sampling: Grain sampling: Water sampling: Hair sampling:

of H u h Arrangements:

Guides:

Institute of Rock and Mineral Analysis Chinese Academy of Geological Sciences Baiwanzhuang Road 26 Beijing 100037 China Td: 0086 10 831 1133 Fax: 0086 10 8320365

b b

Institute of Epidemic Prevention Department of Public Health Enshi

6.

L b

British Geological Survey Key worth Nottingham NG 12 5GG U K Tcl: 0044 (0) 1 159 36322 1 Fax: 0044 (0) 1 159 363329 Em ail: fm CO w po. ncrc.ac. uk

Mr Hu, Villagc: Doctor, Luojiaba ProC Zhang, Dr Su and Ms Fordycc ProC Mao and Ms Gc Ms Ge and Ms Fordycc Prof Mao and Ms Gc

Mr Wu Bcn Chao, Vice Mayor, Enshi City Mr Wang, Director, Ba-jiao Community ProC Zhang, Dr Su and Ms Fordyce Ms Ge Ms Gc and Ms Fordyce Prol' Mao with local hair dresser

Mr Wu Ben Chao; Mr Huuig, Director, Shadi Community; Mr Fuj, Dcputy Dircctor 0 1 Shadi Community and Mr He, Secretary of Shadi Community. Mr Wu Ben Chao uid Mr Fa-j Prol' Zhung, Dr Su, Ms Gc: and Ms Fordyce and Mr Wu Ms Gc and Mr Fa.; Ms Gc and Ms Fordycc ProC Mao and Mr Faj with local hair dresser

Mr Wu Ben Chao; Mr Humg, Director, Shadi Community; Mr Faj, Dcputy Director ol Shadi Community and Mr He, Secretary of Shadi Communily. Mr Wu Ben Chao, Mr Faj and local oflicials from Huabci village

Soil sampling: Grain sampling: Water sampling: Hair sampling:

Arrangements:

Guide: Mr Huang Soil sampling: Grain sampling: Water sampling: Hair sampling:

Yu Arrangements: and Guide Soil sampling: Grain sampling: Water sampling: Hair sampling:

Prof Zhang, Dr Su, Ms Fordyce and Mr w u Ms Ge, Mr Wu and Mr Faj Ms Ge and Ms Fordyce Prof Mao, Ms Ge and Mr Faj with local hair dresser

Mr Zhang, Director, Xin Tang Community and Mr Huang, Secretary, Xin Tang Community.

Prof Zhang, Dr Su, Ms Fordyce and Mr zhang Ms Ge and Mr Zhang Ms Ge and Ms Fordyce Prof Mao with local hair dresser

Mr Xu, Director, Shuang He Community

Prof Zhang, Dr Su and Ms Fordyce Ms Ge and Mr Xu Ms Ge and Ms Fordyce Prof Mao, Ms Ge with local hair dresser

Arrangements: and Guide Soil sampling: Grain sampling: Water sampling: Hair sampling:

Mr Luo, Secretary of Shunmuying Community

Prof Zhang, Dr Su, Ms Ge, Ms Fordyce and Mr Luo Ms Ge and Mr Luo Ms Ge and Ms Fordyce Prof Mao with local hair dresser

Arrangements: and Guides Soil sampling: Grain sampling: Water sampling: Hair sampling:

Mr Luo and local officials from Fangjiaping village

Prof Zhang, Dr Su, Ms Ge and Ms Fordyce Ms Ge and Mr Luo Ms Ge and Ms Fordyce Prof Mao and Ms Ge with local hair dresser

Arrangements: Guide: Soil sampling: Grain sampling: Water sampling : Hair sampling:

Mr Cheng, Director, Xuan ‘en County Mr Yu, Xuan ‘en County Government Office Dr Su, Ms Ge and Ms Fordyce Prof Mao and Ms Ge Ms Ge and Ms Fordyce Prof Mao and Prof Zhang with local hair dresser

Arrangements: Guides:

Soil sampling: Grain sampling: Water sampling: Hair sampling:

Arrangements: Guides:

Director of Public Health, Lichuan County Mr Cheng 1, Director of the Public Hospital, Mou Dao Mr Cheng2, Public Health Department, Lichuan County Prof Zhang, Dr Su, Ms Ge, Ms Fordyce and Mr Cheng Ms Ge and Mr Cheng Ms Ge, Ms Fordyce and Mr Cheng Prof Mao and Mr Cheng* with local hair dresser

Director of Public Health, Lichuan County Mr Chengl, Director of the Public Hospital, Mou Dao

of 7.hi h

40

Mr Cheng2, Public Health Department, Lichuan County Prof Zhang, Dr Su, Ms Ge, Ms Fordyce and Mr Cheng Ms Ge, Prof Mao and Mr Cheng* Ms Ge and Ms Fordyce Prof Mao and Mr Cheng* with local hair d m r

Soil sampling: Grain sampling: Water sampling: Hair sampling:

T i t o r Arrangements: of Public Health, Lichuan County Guides: Mr Cheng 1 , Director of the Public Hospital, Mou Dao

Mr Cheng2, Public Health Department, Lichuan County Soil sampling: Dr Su, Ms Ge, Ms Fordyce and Mr Cheng Grain sampling: Ms Ge and Mr Cheng* Water sampling: Ms Ge and Ms Fordyce Hair sampling: Prof Mao, Prof Zhang and Mr Cheng* with local hair dresser

Arrangements: Dircctor of Public Health, Lichuan County Guides: Mr Chengl, Director of the Public Hospital, Mou Dao

Mr Cheng2, Public Health Department, Lichuan County Soil sampling: Prof Zhang, Dr Su, Ms Ge, Ms Fordyce and Mr Cheng Grain sampling: Prof Zhang and Ms Ge Water sampling: Ms Ge and Ms Fordyce Hair sampling: Prof Mao, Prof Zhang and Mr Cheng* with local hair dresser

of NanEu

Arrangements: Guides:

Soil sampling: Grain sampling: Water sampling: Hair sampling:

Director of Public Health, Lichuan County Mr Cheng2, Public Health Department, Lichuan County Headman of Ji Chang village Prof Zhang, Dr Su, Ms Ge, Ms Fordyce and Mr Cheng Ms Ge and Mr Cheng Ms Ge and Ms Fordyce Prof Mao with local hair dresser

Arrangements: Guide: Soil sampling: Grain sampling: Water sampling: Hair sampling:

Director of Public Health, Lichuan County Mr Cheng2, Public Health Department, Lichuan County Prof Zhang, Dr Su, Ms Ge, Ms Fordyce and Mr Cheng Ms Ge and Mr Cheng Ms Ge and Ms Fordyce Prof Mao with local hair dresser

41

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APPENDIX G . LIST OF SAMPLING EQUIPMENT

Supplied by the BGS Ceocheiiiistiy Ci.oiiy:

aluminium carrying cue portable pH/Eh m e w - (HI 9024/ HI 9025) Hanna Instruments Watcr-resistant Microprocessor portable conductivity meer - (HI 933 100) Hanna Instruments Portable Microprocessor Conductivity Meer spare AAA meter batteries Eh electrode - (Model 96-78-00) Oiion Research Platinum Redox Electrode temperature probe 2 pH electrodes - Russcl pH Limitcd Combination pH Electrodes pH buffer solutions 4.01, 7.01 and 10.01. deionised water wash bottle sectional Dutch auger 200 grey 49x75mm sccuiitaincrs and white lids 85 30ml NalgencO bottles 5 250 ml polyethylcne bicarbonate bottlcs 15 30 ml SeralinO tubes 4 syringes 12 25mm SwincxO liltcr cartridges 100 0.45 pm MillipoicO ccllulosl: acetate tillers digital titmtor - (Model 16900-01) Cainlab Hach bromocresol indicator 2 0.16N and 2 1.6N HSO, Camlab litrator cartridges 100 KraftO paper soil bags 100 small self-seal plastic bags box of tissues 100 blank iicld foilms random number list 2 mm mesh scrccn hand brush for cleaning sieve sieve repair kit 3 black marker pens compass and hand lens

Supplied by J Wrugg (ACG) ill 60iril N( i lgo i i t~ 0 bottlrs:

conductivity svandard 12.86 inS/cm Zobelles Eh calibration solution pH electrode storage solution Oiion AgCl electrode lilling solu~ioii 90-00- 1 I

63

Concentrated ARISTAR grade HNO, Concentrated ARISTAR giadc HCI

Supplied by the IRMA: 160 cloth sample bags 50 ml glass measuring cylindcr 500 ml glass conical l l u k 100 ml plastic bottles

,

APPENDIX H. WATER CHEMISTRY PROCEDURES FOR EQUIPMENT LISTED IN APPENDIX G.

pH and Temperature

1.

2.

3.

4.

5 .

6 .

7.

8 .

9.

10.

Remove the protective cap from the pH electrode and check that no air bubbles are trapped in the bulb at the end of the electrode. If air is present in the bulb, shake the electrode like a thermometer to remove the air. Connect the electrode and the temperatwe probe to the portable pHEh meter. Rinse the electrode and probe thoroughly with deionised water and dry them.

Switch on the meter holding the odoff button for a few seconds until the LCD display appears.

To calibrate the meter press the CAL button. The meter is now expecting the 4.01 calibration buffer solution. The first buffer solution measured during calibration is usually 7.01 therefore use the up arrow button to flick through the buffer solution options until 7.01 is selected. The meter is now ready to begin the calibration.

Place the pH electrode and the temperature probe in the first buffer (7.01) and wait for the reading to stabilise. The meter initially indicates that the reading is NOT READY and will flash a READY signal when the reading has stabilised. Once the READY signal has appeared and the reading is stable press the CFM (confirm) button. Record the pH and temperature readings.

The meter automatically expects the second buffer solution. Use the up and down arrow buttons to flick through the buffer solution options until the c o m t solution is selected (usually 4.01 for acid samples or 10.01 for alkaline samples). The meter is now ready to continue the calibration.

Rinse the electrode and temperature probe thoroughly in deionised water and dry them. Place the electrode and probe in the second buffer solution and wait for the READY signal before pressing the CFM (confirm) button. Note the pH reading. The calibration is now complete and the meter automatically switches to pH measurement mode.

To check the calibration, rinse the electrode and probe in deionised water, dry and return to the first buffer solution. The reading should stabilised around 7.01.

Rinse the electrode and temperature probe thoroughly in deionised water and dry them before measuring the first sample. Rinse the electrode and probe with some of the sample water in-between measuring each sample.

Store the pH electrode with the protective cap containing pH electrode storage solution over the end. Do not allow it to dry out. Care must be taken to avoid damage to the bulb at the end of the electrode.

If the electrode performance is not satisfactory on calibration try shaking it to remove ~y air from the bulb.

65

Redox Potential

1.

2.

3.

4.

5 .

6.

7 .

Remove the protective cap from the redox (Eh) electrode and uncover the filling hole. Fill the electrode using Orion filling solution 9o-00-11 to just below the filling hole. Empty the solution to waste by pushing the cap and body together and refill with solution ensuring that no bubbles are trapped around the electrode base. Connect the electrode and the temperature probe to the pWEh meter. Rinse the electrode and probe in &ionised water and dry them.

Switch on the meter holding the odoff button for a few seconds until the LCD display appears.

Select the redox measurement function by pressing the RANGE button, mV will appear on the display.

To check the electrode performance place the electrode and probe in Zobelles solution. The value should settle between 200 and 250 mV, depending on the temperature.

Rinse the electrode and temperature probe thoroughly in deionised water and dry them before measuring the first sample. Rinse the electrode and probe with some of the sample water in-between measuring each sample.

The readings obtained require correction to redox potential relative to the standard hydrogen electrode according to the formula:

Corrected Eh = Measured Eh + (224 - Temperature "C)

Prior to storage the electrode should be emptied and rinsed with deionised water. Store the electrode dry with the protective cap in place. A small amyount of electrode storage solution should be added to the cap before storage.

66

Total Alkalinity

1.

2.

3.

4.

5 .

6 .

7.

8 .

9.

10.

Select a sulphuric acid cartridge 1.6N or 0.16N according to the expected alkalinity of the samples.

Fit the cartridge to the hand held digital titrator and push the titrator piston down until it meets the top of the cartridge. Remove the cap from the cartridge and fit a feeder straw into the end of the cartridge. Wind the large wheel on the titrator until all the air is removed from the cartridge and the straw and a drop of acid leaves the end of the straw. Wipe the end of the straw to remove excess acid. Reset the titrator scale to WO by winding the small wheel to the left of the scale forwards.

Rinse the measwing cylinder and conical flask with deionised water prior to rinsing them with a small amount of the first sample. Using the measuring cylinder, measure 100 ml of the first sample into the conical flask.

Make sure the lid is securely tightened on the sample bottle in-between each stage of the measurements to reduce degassing of the samples.

Add a few (two) drops of bromocresol green indicator using a small pipette.

Add the acid using the large wheel on the titrator until the solution changes from blue to green-yellow and nok the reading on the titrator scale when this occurs.

When the 0.16N cartridge is used the readings should be multiplied by 0.1.

The reading is the total alkalinity expressed as mg/l CaCO,.

The titrator should be reset to zero and the conical flask and measuring cylinder rinsed in a small amount of the next sample prior to the next measurement.

Titrations should be canied out as quickly as possible to reduce degassing effects .

67

Conductivity

1.

2.

3.

4.

5 .

6.

7.

8 .

Remove the plastic cover from the conductivity probe and rinse the probe and the cover in deionised water. Dry the probe and the cover and replace the cover. Connect the conductivity probe to the conductivity meter.

Switch on the meter and place the probe in the 12.88 mS. calibration buffer solution making sure the solution covers the probe up to the join between the probe and the cover. The holes in the cover must be immersed in the solution.

Shake the probe in the solution to remove any air bubbles trapped between the probe and the cover. This is important as the probe measures conductivity in the volume of affect the readings.

defmd by the cover therefoE & trapped in the cover will

hess the CAL button and the 1413 pS indicator will be lit on the LCD display. Press the BUF button to change to the 12.88 mS calibration.

When the reading is stable and the calibration is within +/- 15% of the ideal value the BUF indicator on the display stops flashing and the CON indicator appears on the display. When the CON indicator appears press the CFM (confirm) button. The meter is now calibrated and will automatically return to measurement mode. To quit from calibration mode at any time press the CAL button.

Remove the plastic cover from the probe, rinse with deionised water and dry the probe and the cover prior to measuring each sample. Remember to cover the probe with sample up to the join between the cover and the probe and to remove air by shaking the probe.

The probe and cover should be rinsed in deionised water and dried before storage.

If the meter is difficult to calibrate try shaking the probe to rcmove air trapped under the cover.

68