Determination of dioxins and polychlorinated biphenyls in breast milk, maternal blood and cord blood from residents of Tohoku, Japan

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) are bioaccumulative chemicals that are considered to be toxic contaminants based on several epidemiological studies. To elucidate exposure levels of these chemicals in the present study, concentrations of PCDD/DFs, dioxin-like PCBs (DL-PCBs) and PCBs in breast milk, maternal blood and cord blood obtained from the same participants registered in a birth cohort study in Tohoku, Japan, were measured. Congener-specific analysis revealed several differences in minor congeners of these compounds among the three specimen types, although major congeners were detected in the specimens. The toxicity equivalence quantity concentrations (1998 WHO-TEF) and PCBs in breast milk, maternal blood and cord blood on the whole and on a lipid basis were in the order of breast milk > maternal blood > cord blood. Pearson's correlation coefficients of TEQs and total PCBs among the three specimens were high, with the correlation coefficient of TEQ between breast milk and maternal blood being the highest (r=0.94, p<0.001). On the other hand, the TEQ between breast milk and cord blood was the lowest (r=0.79, p<0.001). Pearson's correlation coefficient between the TEQ and PCBs in each specimen was also high (r=0.82-0.95, p<0.001). The associations of chemical concentrations with maternal age, parity, fish intake, BMI and the rate of body weight increase during pregnancy were analyzed with multiple linear regression analysis. TEQ concentrations and PCBs were negatively associated with parity (p<0.05), and maternal age was positively associated with PCBs (p<0.05). However, the associations with BMI and fish intake during pregnancy were not significant. These results suggest that parity is an important factor affecting the concentrations of dioxins and PCBs in these specimens.     

Chemical partitioning and remobilization of heavy metals from sewage sludge dumped in Dublin Bay

During the disposal of sewage sludge to the marine environment, chemical changes may alter the mobility of trace elements, thus affecting their potential toxicity and availability to marine organisms. Primary sludge from the Ringsend treatment plant in Dublin receives both domestic waste and trade wastes which contain heavy metals, and approx. 250,000 tons per annum is periodically dumped in Dublin Bay. The purpose of this study was to determine changes which may occur in the chemical partitioning of heavy metals in the sludge during disposal. Samples of sludge were collected from the treatment plant in July 1987. Sequential chemical extraction of heavy metals (Cu, Pb, Cd, Zn, Fe, Mn) was carried out in a nitrogen-filled glove box using 1 M ammonium acetate, 1 M sodium acetate, 0.1 M hydroxylamine HCl (pH 2), 0.2 M ammonium oxalate (pH 3), 30% hydrogen peroxide and concentrated HNO₃. Seawater-extractable metal was determined by mixing subsamples of sludge with filtered seawater from Dublin Bay for 2 h. Chemical partitioning of heavy metals among solid phases in the sludge residue was redetermined by sequential chemical extraction. Both sludge and dumpsite sediments were analysed for total heavy metal content and organic content. The sludge was found to be only slightly anaerobic with a water content of 88% and significant concentrations of some metals, notably copper and zinc. Most of the non-residual copper, lead and cadmium was found in the organic/sulphidic fraction of the sludge (hydrogen peroxide extract), while the dominant phase for zinc was the moderately reducible fraction (ammonium oxalate extract) and only iron and manganese had substantial proportions of metal in more labile phases. Agitation with seawater mobilized cadmium and manganese to a significant extent (56 and 43%, respectively) but negligible amounts of copper or lead (0 and 2%, respectively). However, significant changes in solid-phase partitioning of lead and zinc occurred resulting in mobilization from stronglybound to more labile fractions. No deleterious effects were found at the dumpsite but localized effects are possibly due to the increased mobility of zinc, lead and particularly cadmium.     

Pesticide concentrations in maternal and umbilical cord sera and their relation to birth outcomes in a population of pregnant women and newborns in New Jersey

We evaluated in utero exposures to pesticides by measuring maternal and cord serum biomarkers in a New Jersey cohort of pregnant women and the birth outcomes of their neonates. The study was based on 150 women that underwent an elective cesarean delivery at term in a hospital in central New Jersey. We evaluated the following pesticide compounds in both maternal and umbilical cord sera: chlorpyrifos, diazinon, carbofuran, chlorothalonil, dacthal, metolachlor, trifluralin and diethyl-m-toluamide (DEET). Of these compounds, chlorpyrifos, carbofuran, chlorothalonil, trifluralin, metolachlor and DEET were the pesticides most frequently detected in the serum samples. We found high (≥75th percentile) metolachlor concentrations in cord blood that were related to birth weight (3605 g in upper quartile vs 3399 g; p = 0.05). We also observed an increase in abdominal circumference with increasing cord dichloran concentrations (p = 0.031). These observations suggest that in utero exposures to certain pesticides may alter birth outcomes.     

Preliminary findings of chemistry and bioaccessibility in base metal smelter slags

Leaching of toxic metals from slag waste produced during smelting of Pb-Zn ores is generally considered to be negligible. A 1.4 million tonne stockpile of slag containing up to 2.5% Pb and other contaminants has accumulated on a smelter site at North Lake Macquarie, New South Wales, Australia, and it has also been freely used within the community for landscaping and drainage projects. It had been suggested that Pb in fine particles derived from the slags may be a potential contributor to the blood Pb of some children in this community, although there is conflicting evidence in the literature for such a hypothesis. Bioaccessibility of lead and selected metals derived from nine slag samples collected from areas of public open space was examined using a relatively simple in vitro gastric dissolution technique. Size analyses of the slag samples demonstrate that finely-sized material was present in the slags which could be ingested, especially by children. The finer-sized particles contain high levels of Pb (6,490-41,400 ppm), along with Cd and As. Pb bioaccessibility of the slags was high, averaging 45% for -250 microm material and 75% for particles in the size range -53+32 microm. Increasing bioaccessibility and Pb concentration showed an inverse relationship to particle size. Almost 100% of Pb would be bioaccessible in the smallest slag particles (<20 microm), which also contained very high Pb levels ranging from 50,000 to 80,000 ppm and thus constitute a potential health hazard for children.     

Nonlinear associations between blood lead in children, age of child, and quantity of soil lead in metropolitan New Orleans

Previous studies identified a curvilinear association between aggregated blood lead (BL) and soil lead (SL) data in New Orleans census tracts. In this study we investigate the relationships between SL (mg/kg), age of child, and BL (μg/dL) of 55,551 children in 280 census tracts in metropolitan New Orleans, 2000 to 2005. Analyses include random effects regression models predicting BL levels of children (μg/dL) and random effects logistic regression models predicting the odds of BL in children exceeding 15, 10, 7, 5, and 3 μg/dL as a function of age and SL exposure. Economic benefits of SL reduction scenarios are estimated. A unit raise in median SL^0.5 significantly increases the BL level in children (b = 0.214 p = < 0.01), and a unit change in Age^0.5 significantly increases child BL (b = 0.401, p = < 0.01). A unit change in Age^0.5 increases the odds of a child BL exceeding 10 μg/dL by a multiplicative factor of 1.23 (95% CI 1.21 to 1.25), and a unit (mg/kg) addition of SL increases the odds of child BL > 10 μg/dL by a factor of 1.13 (95% CI 1.12 to 1.14). Extrapolating from regression results, we find that a shift in SL regulatory standard from 400 to 100 mg/kg provides each child with an economic benefit ranging from $4710 to $12,624 ($US 2000). Children's BL is a curvilinear function of both age and level of exposure to neighborhood SL. Therefore, a change in SL regulatory standard from 400 to 100 mg/kg provides children with substantial economic benefit.     

Surface adsorption of metals onto the earthworm Lumbricus rubellus and the isopod Porcellio scaber is negligible compared to absorption in the body

In terrestrial organisms, bioaccumulation is usually based on a summation of the amount of metal adsorbed to the body wall and absorbed into the body. The relative proportions of metal adsorption and absorption are usually not quantified. In this study, the distinction between adsorbed and absorbed metals was investigated in two different terrestrial species exposed to metals for 2 weeks. The earthworm Lumbricus rubellus was chosen as representative for organisms mainly taking up metals via the dermal route, and the isopod Porcellio scaber as an organism taking up metals mainly via the alimentary tract. Cross-sections of whole animals were made using a cryostat and accumulated metals were localized by means of a phosphor screen (autoradiography). Radiolabels were used to determine the distribution of metals over the different organs and to distinguish between adsorption and absorption. Cd in the earthworm was mainly found in tissues of the chloragogenous region, whereas Zn was also found in various other organs and in the connective tissue. In the isopod, both Cd and Zn were mainly located in the hepatopancreas. Adsorbed amounts of Cd and Zn were negligible compared to internalized Cd and Zn concentrations for both organisms. Consequently, when focusing on effects of metal uptake for the organism itself, there is no need to correct for adsorption. This suggests that adsorption to the epidermis is not a rate limiting step in metal uptake by soil invertebrates.     

Prenatal exposure to lead in Spain: cord blood levels and associated factors

Introduction and Objective

Lead is a known neurotoxic. Fetuses and infants are very vulnerable to lead exposure, since their blood-brain barrier is not completely formed. Hence, there is an importance for monitoring of blood lead levels prenatally and during early infancy. The aim of this study is to evaluate the prenatal exposure to lead and its association with maternal factors in four population based mother-child cohorts in Spain. The present research was carried out within the framework of the INMA project INfancia y Medio Ambiente (Environment and Childhood).

Methods

A total of 1462 pregnant women were recruited between 2004 and 2008. Lead was analyzed in a sample of cord blood by thermal decomposition, amalgation, and Atomic Absorption Spectrometry. Maternal sociodemographic, lifestyle and dietary factors were obtained by questionnaires during pregnancy. A multivariate logistic regression model was constructed. The dependent variable was a dichotomous lead level variable (detected vs no detected, i.e. ≥ vs < 2 μg/dL).

Results

A low percentage of cord blood samples with lead levels ≥ 2 μg/dL were found (5.9%). Geometric mean and maximum were 1.06 μg/dL and 19 μg/dL, respectively. Smoking at the beginning of pregnancy, age, social class, weight gain during pregnancy, gravidity, and place of residence were the maternal factors associated with detectable cord blood lead levels. Mother's diet does not appear to be a determining factor of lead exposure. Nevertheless, daily intake of iron and zinc may act as a protective factor against having cord blood lead levels ≥ 2 μg/dL.

Conclusion

In the different regions of Spain taking part in this study, lead levels to which newborns are exposed are low. Mobilization of lead from bones may be the main contributor to the cord blood levels.     

Age- and size-specific patterns of heavy metals in the organs of freshwater fish Abramis brama L. populating a low-contaminated site

Concentrations of cadmium, copper, mercury, lead and zinc were determined by atomic absorption spectrophotometry in the muscle, gill and liver of bream Abramis brama L. to study the relationship between the heavy metal load of fish and their age and size, and the seasonal variation of pollutant loads. Fish were collected from the Western basin of Lake Balaton (Hungary) in October 1999 and May 2000. The average metal concentrations of different organs varied in the following ranges: Cd 0.42-2.10; Cu 1.77-56.2; Hg 0.01-0.19; Pb 0.44-3.24; Zn 10.9-82.5 microg g(-1) dry weight. The highest Cd, Cu, Pb and Zn concentrations were detected in the gill or liver of fish, whereas the highest Hg concentrations were measured in the muscle. In the liver of bream for cadmium, copper and mercury the Pearson correlation analysis revealed positive associations related to age and size (length, net weight), as well as for the mercury load of all three investigated organs. In the muscle and gill the copper, lead and zinc concentrations, similarly to the lead and zinc concentrations of the liver, the associations related to age and size were negative. The correlations between the heavy metal concentrations of organs and the individual condition factors of fish samples proved to have opposite trends compared to those related to the age and size of fish. The seasonal variations in the heavy metal load of bream could be attributed rather to the seasonal change in the condition factor of fish than to variations in the pollutant load of the site.     

水中重金属离子吸附材料的研究现状与发展趋势

系统介绍了无机吸附材料（碳质类、矿物类、金属氧化物类）、有机高分子吸附材料（纤维素、壳聚糖、农林废弃物、离子交换树脂等）和复合型吸附材料（有机/有机型、无机/无机型、有机/无机型）等重金属离子吸附材料的物化特性和结构特点,对上述材料去除水体典型重金属离子的吸附容量、吸附机理、工程应用进展等进行了综述。阐述了纳米材料、离子选择性材料和可降解生物质材料等新型重金属离子吸附材料的研究现状及发展趋势。结果表明:开发价格低廉、吸附容量高、选择性高、可再生且环境友好的吸附材料是重金属离子吸附研究的重要方向;结合现代化检测技术和分析手段,探索吸附过程中吸附剂与重金属离子间相互作用的本质,对于拓展吸附机理和开发性能优良的吸附材料具有重要的理论和实际意义。     

Concentrations of 17 elements, including mercury, and their relationship to fitness measures in arctic shorebirds and their eggs

Exposure to contaminants is one hypothesis proposed to explain the global decline in shorebirds, and this is of particular concern in the arctic. However, little information exists on contaminant levels in arctic-breeding shorebirds, especially in Canada. We studied potential contaminants in three biparental shorebird species nesting in Nunavut, Canada: ruddy turnstones (Arenaria interpres), black-bellied plovers (Pluvialis squatarola) and semipalmated plovers (Charadrius semipalmatus). Blood, feathers and eggs were analyzed for As, Be, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, Se, Tl, V, and Zn. We assessed whether element concentrations a) differed among species and sexes, b) were correlated among pairs and their eggs, and c) were related to fitness endpoints, namely body condition, blood-parasite load, nest survival days, and hatching success.Non-essential elements were found at lower concentrations than essential elements, with the exception of Hg. Maximum Hg levels in blood approached those associated with toxicological effects in other bird species, but other elements were well below known toxicological thresholds. Reproductive success was negatively correlated with paternal Hg and maternal Pb, although these effects were generally weak and varied among tissues. Element levels were positively correlated within pairs for blood-Hg (turnstones) and feather-Ni and Cr (semipalmated plovers); concentrations in eggs and maternal blood were never correlated. Concentrations of many elements differed among species, but there was no evidence that any species had higher overall exposure to non-essential metals. In conclusion, whereas we found little evidence that exposure to the majority of these elements is leading to declines of the species studied here, Hg levels were of potential concern and both Hg and Pb warrant further monitoring.     

Influence of pH and TOC concentration on Cu,Zn, Cd,and Al speciation in rivers

Dissolved ( < approximately 4 nm, dialysis in situ), colloidal ( < 0.45 microm filtered, minus dissolved) and particulate (total, minus < 0.45 microm filtered) concentrations of Cu, Zn, Cd, (Al) in eight (three) mining polluted rivers were determined by atomic absorption spectrometry (flame and graphite furnace). The metal size distribution in the rivers was compared to pH, Ca concentration, alkalinity, conductivity, and total organic carbon (TOC). Data plots based on the present and other studies also yielded information about the interrelations between TOC, pH and metal adsorption in rivers and lakes. Less than 10% of Cu, Zn, and Cd were sorbed on particles or colloids in two rivers with average pH at 3.1 and 5.1, whereas 46%, 21%, and 21% of Cu, Zn, and Cd, respectively, occurred in sorbed form in six pH neutral rivers. In three pH neutral rivers, on average 55% of Al was in colloidal form, whereas the dissolved and particulate fractions were 21% and 23%, respectively. Our data combined with data from similar studies support conclusions from other research suggesting that the percent fraction of metals adsorbed on particles rises steeply from almost zero to nearly 100% within a narrow and element specific pH range. Changes in TOC concentration seem capable of shifting the pH to % metal absorption curves in the order of one pH unit.     

Distribution of polychlorinated biphenyls, organochlorine pesticides and polybrominated diphenyl ethers in human umbilical cord serum, maternal serum and milk from Wielkopolska region, Poland

The levels of organochlorinated pesticides (OCPs): p,p'-DDT and its metabolites, hexachlorobenzene (HCB), hexachlorocyclohexane isomers (HCHs), chlordanes and their metabolites, and 18 polychlorinated biphenyl (PCB) congeners were measured in maternal serum, umbilical cord serum and human milk collected from 22 mothers living in the Wielkopolska region, Poland. Additionally, 11 polybrominated diphenyl ether (PBDE) congeners were measured in the human milk samples. p,p'-DDT and its major metabolite, p,p'-DDE, together with HCB, were found in all milk and serum samples. Median concentrations of p,p'-DDE in maternal serum, umbilical cord serum and milk were 343, 329 and 634ng/g lipid weight (lw). PCB congeners 138, 153 and 180 were the major congeners measured in all serum samples, while CB 170 was detected in 74% and 100% of umbilical cord and maternal serum, respectively. Except for CBs 74, 101 and 105, which had a detection frequency of 77%, 23% and 82%, respectively, all investigated PCB congeners were measured in all human milk samples. The median concentrations of sum PCBs in maternal serum, umbilical cord serum and milk were 79, 60 and 133 ng/g lw, respectively. A good correlation (Spearman R(S)>0.75, p<0.001) was found for major PCBs, p,p'-DDT and p,p'-DDE, between maternal and umbilical cord serum, while the correlation was weaker between milk and serum. The median of sum PBDEs in human milk was 2.0 ng/g lw (range 0.8 to 8.4), with BDE 47 being always the most abundant PBDE congener and, together with BDE 153, being present in all samples. In general, results found in the investigated group are at the low end of the concentration range measured in Europe.     

Biomonitorization of cadmium, chromium, manganese, nickel and lead in whole blood, urine, axillary hair and saliva in an occupationally exposed population

Heavy metal contamination from occupational origin is a cause for concern because of its potential accumulation in the environment and in living organisms leading to long term toxic effects. This study was aimed to assess Cd, Cr, Mn, Ni and Pb levels in whole blood, urine, axillary hair and saliva from 178 individuals with occupational exposure to heavy metals. Levels of metal compounds were determined by atomic absorption spectrometry. We collected information on occupation, lifestyle habits and food intake by questionnaire. Multiple linear regression analyses for metal ion concentration in whole blood, urine, axillary hair and saliva were adjusted for age, gender, smoking and alcohol consumption, lifetime workplace exposure, residence area and food habits. Overall, blood and urine median concentrations found for the five metals analyzed do not exceed biological exposure indexes, so that they are very similar to a non-occupationally exposed population. Toxicokinetic differences may account for the lack of correlations found for metal levels in hair and saliva with those in blood or urine. For those heavy metals showing higher median levels in blood with respect to hair (Cd, Mn and Pb) indicating lesser hair incorporation from blood, the lifetime working experience was inversely correlated with their hair levels. The longer the lifetime working experience in industrial environments, the higher the Mn and Ni concentration in saliva. Axillary hair and saliva may be used as additional and/or alternative samples to blood or urine for biomonitoring hair Mn, and saliva Ni in subjects with occupational exposure.     

The intake of lead and associated metals by sheep grazing mining-contaminated floodplain pastures in mid-Wales, UK: II. Metal concentrations in blood and wool

Sheep grazing metal-contaminated floodplain pastures across mid-Wales ingest high concentrations of lead (Pb) in vegetation and directly in the form of soil. Sheep whole blood analysis indicated that Pb concentrations can be significantly elevated for animals grazing contaminated sites: in winter/spring, a median blood concentration of 147 µg Pb l^− 1 was found at the location with the highest soil enrichment of this metal compared to only 26 µg Pb l^− 1 for the control flock. There was within-flock variability in blood-Pb concentration, and overlap between blood-Pb ranges in animals grazing control and contaminated sites, although use of the Kruskal-Wallis H test established a number of significant (P < 0.05) differences between the blood-Pb content of flocks grazing the various study locations. Despite total daily intakes of up to 723 mg Pb d^− 1, only one individual sheep showed a blood-Pb content above the ‘normal safe’ concentration of 250 µg l^− 1. Blood and wool analyses were found to have limited value for the diagnosis of environmental exposure to Pb, and further consideration of metal accumulation in offal, bone and muscle tissue is recommended.     

Perinatal lead and mercury exposure in Austria

Objective

The heavy metals lead (Pb) and mercury (Hg) are ubiquitous environmental pollutants with high neurotoxic potential. We aimed to compare perinatal Pb and Hg concentrations and to explore the potential association between Pb and Hg exposure and newborn anthropometry.

Study design

Pregnant women were recruited in 2005 at the General Hospital Vienna for participation in this longitudinal study. Pb and Hg concentrations were measured in maternal blood and hair, placenta, cord blood, meconium, and breast milk of 53 mother-child pairs by CV-AAS, GF-AAS, and HPLC-CV-ICPMS. We conducted bivariate analyses and categorical regression analysis (CATREG) to evaluate the determinants of Pb and Hg exposure, and of infant anthropometry.

Results

Median Pb and total Hg contents were low, i.e., 25 μg/L (maternal blood-Pb), 13 μg/L (cord blood-Pb), 0.7 μg/L (maternal blood-Hg), and 1.1 μg/L (cord blood-Hg). Hg levels in maternal and fetal tissues were frequently correlated (r > 0.3, P < 0.05, respectively). Regarding Pb, only maternal blood and cord blood concentrations correlated (P = 0.043). Cord blood levels indicated higher Hg exposure but lower Pb exposure relative to maternal blood contents. Adjusted CATREG models indicated the significant predictors of birth length (placenta-Pb, gestational length, meconium-Pb), birth weight (placenta-Pb, gestational length, maternal blood-Pb), and head circumference (maternal education, maternal height). Besides one significant correlation between maternal hair Hg and birth length, the mercury levels were not associated with newborn anthropometry.

Conclusions

Our data implicate that different modes of action may exist for placentar transfer of Pb and Hg as well as that low Pb exposure levels can result in lower birth weight. The findings related to newborn anthropometry need to be confirmed by the examination of larger study groups. Further research is needed to clarify the mechanisms of Pb and Hg transfer via the placenta, and to explore how prenatal Pb exposure is related to intrauterine growth.     

Sources and timing of anthropogenic pollution in the Ensenada de San Simon (inner Ria de Vigo), Galicia, NW Spain: an application of mixture-modelling and nonlinear optimization to recent sedimentation

The Ensenada de San Simon is the inner part of the Ria de Vigo, one of the major mesotidal rias of the Galician coast, NW Spain. The geochemistry of its bottom sediments can be accounted for in terms of both natural and anthropogenic sources. Mixture-modelling enables much of the Cr, Ni, V, Cu, Pb and Zn concentrations of the bottom and subaqueous sediments to be explained by sediment input from the river systems and faecal matter from manmade mussel rafts. The compositions and relative contributions of additional, unknown, sources of anomalous heavy-metal concentrations are quantified using constrained nonlinear optimization. The pattern of metal enrichment is attributed to: material carried in solution and suspension in marine water entering the Ensenada from the polluted industrial areas of the adjacent Ria de Vigo; wind-borne urban dusts and/or vehicular emissions from the surrounding network of roads and a motorway road-bridge over the Estrecho de Rande; industrial and agricultural pollution from the R. Redondela; and waste from a former ceramics factory near the mouth of the combined R. Oitaben and R. Verdugo. Using (137)Cs dating, it is suggested that heavy metal build-up in the sediments since the late 1970s followed development of inshore fisheries and introduction of the mussel rafts (ca. 1960) and increasing industrialisation.     

Cadmium solubility in paddy soils: effects of soil oxidation, metal sulfides and competitive ions

Cadmium (Cd) is a non-essential element for human nutrition and is an agricultural soil contaminant. Cadmium solubility in paddy soils affects Cd accumulation in the grain of rice. This is a human health risk, exacerbated by the fact that rice grains are deficient in iron (Fe) and zinc (Zn) for human nutrition. To find ways of limiting this potential risk, we investigated factors influencing Cd solubility relative to Fe and Zn during pre-harvest drainage of paddy soils, in which soil oxidation is accompanied by the grain-filling stage of rice growth. This was simulated in temperature-controlled “reaction cell” experiments by first excluding oxygen to incubate soil suspensions anaerobically, then inducing aerobic conditions. In treatments without sulfur addition, the ratios of Cd:Fe and Cd:Zn in solution increased during the aerobic phase while Cd concentrations were unaffected and the Fe and Zn concentrations decreased. However, in treatments with added sulfur (as sulfate), up to 34 % of sulfur (S) was precipitated as sulfide minerals during the anaerobic phase and the Cd:Fe and Cd:Zn ratios in solution during the aerobic phase were lower than for treatments without S addition. When S was added, Cd solubility decreased whereas Fe and Zn were unaffected. When soil was spiked with Zn the Cd:Zn ratio was lower in solution during the aerobic phase, due to higher Zn concentrations. Decreased Cd:Fe and Cd:Zn ratios during the grain filling stage could potentially limit Cd enrichment in paddy rice grain due to competitive ion effects for root uptake.