Geochemical associations and availability of cadmium (Cd) in a paddy field system, Northwestern Thailand

Abstract

The Mae Tao watershed, northwestern Thailand, has become contaminated with cadmium (Cd) from the zinc mining activities area in the nearby Thanon-Thongchai mountains. Consumption of Cd-contaminated rice has led to documented human health impacts. The aim of this study was to clarify transfer pathways from creek and canal waters to the paddy field soils near Baan Mae Tao Mai village and to determine the relationship between Cd forms in the soil and uptake by rice plants. Soils, irrigation canal sediments and water samples were collected during the dry season and at the onset of the rainy season. Rice samples were collected at harvesting time and samples of soil fertiliser were also obtained. Water samples were filtered, ultrafiltered and analysed by ICP-MS whilst sub-samples of dried, ground soils and sediments were first subjected to micro-wave assisted acid digestion (modified US EPA method 3052). XPRD and SEM-EDX methods were used for mineralogical characterisation and selective chemical extractions have assisted in the characterisation of solid phase Cd associations. Transfer mainly occurred in association with particulate matter during flooding and channel dredging and, in contrast with many other studies, most of the soil Cd was associated with exchangeable and carbonate-bound fractions. Moreover, there was a significant positive relationship between soil total Cd and rice grain Cd (R2=0.715), but a stronger relationship between both the Tessier-exchangeable soil Cd and the BCR-exchangeable soil Cd and rice grain Cd (R2=0.895 and 0.861, respectively). Stable Isotope Exchange (gives isotopically exchangeable Cd - E value) is generally considered to provide a better measure of bioavailability. The results of this study showed that SIE gave values which significantly positive correlated with the Tessier exchangeable fraction. Biochar has a porous structure and acidic functional groups on its surface which give it a high capacity to affect heavy metal adsorption when added to soils. Biochar samples were produced from rice husk (RHC) and miscanthus (MC) since these are cheap and readily available materials in Thailand. Indeed rice husk char is already used for rice seed germination by local farmers. Evaluation of the chemical and physical properties of the chars showed that the lower temperature (350°C) chars had greater proportions of oxygen-containing functional groups than those produced at 700°C. Moreover the low temperature RHC had the greater cation exchange capacity than the MC produced at the same temperature. In abiotic feasibility tests, it was shown that RHC was more effective than MC at lowering soil available Cd. The former reduced the E values for the medium-Cd soils by 4.7% and 16.0% when 1% and 5% RHC, was added, respectively. From pot experiments, in medium-Cd soils, 1% and 5% RHC amendment showed the potential to decrease Cd uptake by rice roots. However, further work involving addition of a greater proportion of biochar with a higher number of replicates is needed to reach more robust conclusions.