Derivation and validation of thresholds of cadmium, chromium, lead, mercury and arsenic for safe rice production in paddy soil.

Cadmium (Cd), chromium (Cr), lead (Pb), mercury (Hg) and arsenic (As) are potent toxicants to human health via dietary intake. It is imperative to establish accurate soil thresholds based on soil-plant transfer models and food safety standards for safe agricultural production. This study takes rice genotypes and soil properties into account to derive soil thresholds for five heavy metal(loid)s using the bioconcentration factors (BCF) and species sensitivity distribution (SSD) based on the food safety standard. The BCF generated from two paddy soils was calculated to investigate the sensitivity of heavy metal accumulation in nine rice cultivars in a greenhouse pot experiment. Then, empirical soil-plant transfer models were developed from a middle-sensitivity rice cultivar (Denong 2000, one selected from nine rice) grown in nineteen paddy soils with various soil properties under a proper exogenously metal(loid)s concentration gradient. After normalization, hazardous concentrations from the fifth percentile (HC5) were calculated from the SSD curves, and the derived soil thresholds were obtained from HC5 prediction models that based on the combination of pH and organic carbon (OC) or cation exchange capacity (CEC). The soil Cd threshold derived based on pH and organic carbon (pH < 7.5, OC ≥ 20 g kg-1) was 1.3-fold of those only considering pH, whereas the Pb threshold (pH > 6, CEC ≥ 20 cmolc kg-1) was 3.1 times lower than the current threshold. The derived thresholds for five elements were validated to be reliable through literature data and field experiments. The results suggested that deriving soil heavy metal(loid)s threshold using SSD method and local food safety standards is feasible and also applicable to other crops as well as other regions with potential health risks of toxic elements contamination in agricultural production.

Evolution of As speciation with depth in a soil profile with a geothermal As origin.

High contents of arsenic were detected in soils in Guandu plain, northwest Taiwan. To determine the sources and speciation of As in the soils, the depth profiles of soil properties, elemental composition and As speciation were investigated. The As concentrations in the soil profile ranged from 152 to 1222 mg kg-1, with the highest concentration at the depth of 70-80 cm. The As distribution was found to be positively correlated to Fe, Pb, and Ba. The As(V)-adsorbed ferrihydrite and scorodite were the predominant phases in the top layers (<50 cm), while beudantite was the predominant phase below 50 cm along with As(III)- and As(V)-adsorbed ferrihydrite as the minor components. The results of sequential extraction showed that As-associated with noncrystalline and crystalline Fe/Al hydrous oxides and residual phases were predominant at the depths of 0-60, 60-100 and 100-140 cm, respectively, indicating an increasing As recalcitrance with soil depth. Based on the soil properties, and elemental and mineral compositions at different soil depths, the origin of beudantite in the soils was likely allogenic rather than authigenic or anthropogenic. The formation of scorodite in the surface soils was suggested to be transformed from beudantite. As-associated Fe hydrous oxides may be contributed by the progressive dissolution of beudantite and scorodite, and the continuous influxes of As and Fe. While Fe hydrous oxides were able to immobilize As during the dissolution of As-bearing minerals, the increase of As mobility in soils may imply an increase in the environmental risk of As over time.

Lung Cancer Risk and Low (≤50 µg/L) Drinking Water Arsenic Levels for US Counties (2009⁻2013)-A Negative Association.

While epidemiologic studies clearly demonstrate drinking water with high levels of arsenic as a significant risk factor for lung cancer, the evidence at low levels (≤50 µg/L) is uncertain. Therefore, we have conducted an ecological analysis of recent lung cancer incidence for US counties with a groundwater supply of.

The Case for Universal Screening of Private Well Water Quality in the U.S. and Testing Requirements to Achieve It: Evidence from Arsenic.

BACKGROUND: The 1974 Safe Drinking Water Act (SDWA) regulates >170,000 public water systems to protect health, but not >13 million private wells. State and local government requirements for private well water testing are rare and inconsistent; the responsibility to ensure water safety remains with individual households. Over the last two decades, geogenic arsenic has emerged as a significant public health concern due to high prevalence in many rural American communities. OBJECTIVES: We build the case for universal screening of private well water quality around arsenic, the most toxic and widespread of common private water contaminants. We argue that achieving universal screening will require policy intervention, and that testing should be made easy, accessible, and in many cases free to all private well households in the United States, considering the invisible, tasteless, odorless, and thus silent nature of arsenic. DISCUSSION: Our research has identified behavioral, situational and financial barriers to households managing their own well water safety, resulting in far from universal screening despite traditional public health outreach efforts. We observe significant socioeconomic disparities in arsenic testing and treatment when private water is unregulated. Testing requirements can be a partial answer to these challenges. CONCLUSIONS: Universal screening, achieved through local testing requirements complemented by greater community engagement targeting biologically and socioeconomically vulnerable groups, would reduce population arsenic exposure greater than any promotional efforts to date. Universal screening of private well water will identify the dangers hidden in America's drinking water supply and redirect attention to ensure safe water among affected households. https://doi.org/10.1289/EHP629.

Levels of infants' urinary arsenic metabolites related to formula feeding and weaning with rice products exceeding the EU inorganic arsenic standard.

Early childhood inorganic arsenic (i-As) exposure is of particular concern since it may adversely impact on lifetime health outcomes. Infants' urinary arsenic (As) metabolites were analysed in 79 infants by inductively coupled plasma-mass spectrometric detection (IC-ICP-MS) to evaluate i-As exposure pre- and post-weaning. Levels of i-As in rice-based weaning and infants' foods were also determined to relate to urinary As levels. Higher As levels, especially of monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA), were found in urine from formula fed infants compared to those breastfed. Urine from infants post-weaning consuming rice-products resulted in higher urinary MMA and DMA compared to the paired pre-weaning urine samples. The European Union (EU) has regulated i-As in rice since 1st January 2016. Comparing infants' rice-based foods before and after this date, little change was found. Nearly ¾ of the rice-based products specifically marketed for infants and young children contained i-As over the 0.1 mg/kg EU limit. Efforts should be made to provide low i-As rice and rice-based products consumed by infants and young children that do not exceed the maximum i-As level to protect this vulnerable subpopulation.

Synthesis of diatom-FeOx composite for removing trace arsenic to meet drinking water standards.

This study presents the synthesis of diatom-FeOx composite as a novel sorbent for arsenic removal from water. The unique porous architecture of the diatom was utilized to immobilize iron oxide to form the composite. The surface area was as high as 70 m(2)/g. The adsorption isotherms for As (III) and As (V) followed the Langmuir, Freundlich and D-R models. Langmuir monolayer adsorption capacity for arsenite (As III) was 10,000 µg/g and arsenate (As V) was 12,500 µg/g. The pseudo-second order rate equation was found to effectively describe the kinetics of arsenic adsorption. This study opens the door for the development of bio derived materials for environmental remediation.

Dietary intake of trace elements by the population of Catalonia (Spain): results from a total diet study.

This study aimed to analyse the concentrations of Al, Ba, Bi, Cu, Cr, Ge, Mn, Mo, Ni, Sb, Se, Sr and Zn in food samples collected in 2008 in Catalonia (Spain). The dietary intake of these 13 trace elements was subsequently estimated by different age-gender groups of the population: children, adolescents, adults and seniors. In general terms, fish and shellfish, cereals, and pulses were the food groups showing the highest levels for most elements. Higher dietary intakes were associated with male groups (adolescents, adults and seniors). However, none exceeded the tolerable levels. When exposure was estimated based on body weight, children were the group with the highest dietary intake. Notwithstanding, only the weekly intake of Al by children exceeded the recommendations of the European Food Safety Authority (EFSA). It is a consequence of the higher intake of cereals in relation to their respective body weights. In addition to the periodical food surveillance of toxic metals (As, Cd, Hg and Pb), it is also important to determine the levels of other trace elements in order to ensure that the dietary exposure by the Catalan population is under control.

Certification of a reference material of metal content in atmospheric particles deposited on filters.

Air quality is one of the areas in Europe where a series of EU Directives have been published with the aim of achieving improved long-term and harmonised air quality objectives across the European Union. This paper describes the production of a certified reference material, aiming to support QA/QC programmes of analytical laboratories in the framework of the air quality monitoring activities. The certified values are the As, Cd, Ni and Pb masses in PM10 particles deposited on quartz filters (CRM SL-MR-2-PSF-01). All the steps of the certification, i.e. the material characterisation, homogeneity and stability evaluation and uncertainty calculation, were performed according to the ISO guide 35 guidelines. The certification was conducted using the characterisation by a single method approach based on isotope dilution for cadmium, nickel, and lead and gravimetric standard addition calibration for arsenic associated with inductively coupled mass spectrometry (ICP-MS). The amounts of the four elements are in the range of the target values regulated by EU Directives.

Use of mode of action data to inform a dose-response assessment for bladder cancer following exposure to inorganic arsenic.

In the recent National Research Council report on conducting a dose-response assessment for inorganic arsenic, the committee remarked that mode of action data should be used, to the extent possible, to extrapolate below the observed range for epidemiological studies to inform the shape of the dose-response curve. Recent in vitro mode of action studies focused on understanding the development of bladder cancer following exposure to inorganic arsenic provide data to inform the dose-response curve. These in vitro data, combined with results of bladder cancer epidemiology studies, inform the dose-response curve in the low-dose region, and include values for both pharmacokinetic and pharmacodynamic variability. Integration of these data provides evidence of a range of concentrations of arsenic for which no effect on the bladder would be expected. Specifically, integration of these results suggest that arsenic exposures in the range of 7-43 ppb in drinking water are exceedingly unlikely to elicit changes leading to key events in the development of cancer or noncancer effects in bladder tissue. These findings are consistent with the lack of evidence for bladder cancer following chronic ingestion of arsenic water concentrations <100 ppb in epidemiological studies.

The relevance of physicochemical and biological parameters for setting emission limit values for plants treating complex industrial wastewaters.

The influents of plants treating complex industrial wastewaters from third parties may contain a large variety of often unknown or unidentified potentially harmful substances. The conventional approach of assessing and regulating the effluents of these plants is to set emission limit values for a limited set of physicochemical parameters, such as heavy metals, biological oxygen demand, chemical oxygen demand and adsorbable organic halogen compounds. The objective of this study was to evaluate the relevance of physicochemical parameters for setting emission limit values for such plants based on a comparison of effluent analyses by physicochemical and biological assessment tools. The results show that physicochemical parameters alone are not sufficient to evaluate the effectiveness of the water treatment plants for removing hazardous compounds and to protect the environment. The introduction of toxicity limits and limits for the total bioaccumulation potential should be considered to supplement generic parameters such as chemical oxygen demand and adsorbable organic halogens. A recommendation is made to include toxicity screening as a technique to consider in the determination of best available techniques (BAT) during the upcoming revision of the BAT reference document for the waste treatment industries to provide a more rational basis in decisions on additional treatment steps.

Trace metal source terms in carbon sequestration environments.

Carbon dioxide sequestration in deep saline and depleted oil geologic formations is feasible and promising; however, possible CO(2) or CO(2)-saturated brine leakage to overlying aquifers may pose environmental and health impacts. The purpose of this study was to experimentally define a range of concentrations that can be used as the trace element source term for reservoirs and leakage pathways in risk simulations. Storage source terms for trace metals are needed to evaluate the impact of brines leaking into overlying drinking water aquifers. The trace metal release was measured from cements and sandstones, shales, carbonates, evaporites, and basalts from the Frio, In Salah, Illinois Basin, Decatur, Lower Tuscaloosa, Weyburn-Midale, Bass Islands, and Grand Ronde carbon sequestration geologic formations. Trace metal dissolution was tracked by measuring solution concentrations over time under conditions (e.g., pressures, temperatures, and initial brine compositions) specific to the sequestration projects. Existing metrics for maximum contaminant levels (MCLs) for drinking water as defined by the U.S. Environmental Protection Agency (U.S. EPA) were used to categorize the relative significance of metal concentration changes in storage environments because of the presence of CO(2). Results indicate that Cr and Pb released from sandstone reservoir and shale cap rocks exceed the MCLs by an order of magnitude, while Cd and Cu were at or below drinking water thresholds. In carbonate reservoirs As exceeds the MCLs by an order of magnitude, while Cd, Cu, and Pb were at or below drinking water standards. Results from this study can be used as a reasonable estimate of the trace element source term for reservoirs and leakage pathways in risk simulations to further evaluate the impact of leakage on groundwater quality.

A baseline study of levels of mercury, arsenic, cadmium and lead in Northeast Arctic cod (Gadus morhua) from different parts of the Barents Sea.

This study is one of several baseline studies that will provide basic and reliable information about the content of undesirable substances in important species of fish caught in Norwegian waters. Concentrations of metals in the muscle and liver of more than 800 Northeast Arctic cod caught at 32 sites in the Barents Sea are reported. The highest concentration of both mercury in the muscle and cadmium in the liver was found in cod caught in the western part of the Barents Sea, while the highest concentration of total arsenic was found in cod from the eastern part. The arsenic concentrations varied greatly among individual fish, ranging from 0.3 to 170 mg kg(-1) wet weight in the muscle. Such high levels of total arsenic have never previously been reported in any fish, and the primary factor for these high concentrations is likely to be the shrimp in the cod diet.

Development of a certified reference material (NMIJ CRM 7531-a) for the determination of trace cadmium and other elements in brown rice flour.

A certified reference material (CRM) for trace cadmium and other elements in brown rice flour was developed at the National Metrology Institute of Japan (NMIJ). The CRM was provided as a dry powder after drying and frozen pulverization of fresh brown rice obtained from a Japanese domestic market. Characterization of the property value for each element was carried out exclusively by NMIJ with at least two independent analytical methods, including inductively coupled plasma mass spectrometry (ICP-MS), ICP high-resolution mass spectrometry, isotope-dilution ICP-MS, ICP optical emission spectrometry, and graphite-furnace atomic-absorption spectrometry. Property values were provided for six elements (Mn, Fe, Cu, Zn, As, and Cd). The concentration range of the property values was from 0.280 mg kg(-1) of As to 31.8 mg kg(-1) of Zn. The combined relative standard uncertainties of the property values were estimated by considering the uncertainties of the homogeneity, characterization, difference among analytical methods, dry-mass correction factor, and calibration standard. The range of the relative combined standard uncertainties was from 1.1% of Zn to 1.6% of As.

Arsenic and lead in juice: apple, citrus, and apple-base.

Exposure limits for arsenic and lead in drinking water have long been established by the U.S. Environmental Protection Agency and new regulations regarding the presence of these contaminants in bottled water went into effect in California in 2009. No comparable exposure limits or regulations are available, however, for juices and other beverages that may contain arsenic and lead. In the study described in this article, 20 apple juices (or ciders), 15 apple-containing juices, one grape, and one citrus juice were analyzed for arsenic and lead. Arsenic was detected in all juices while lead was detected in more than 94% of juices analyzed. Twelve samples (32%) demonstrated arsenic levels nearly at or above the drinking water exposure limit of 10 parts per billion. No juices contained lead above drinking water exposure limits. Expanding drinking water limits to include juices (and other frequently consumed beverages) would better protect consumers while regular testing of these juices would better inform consumers of the risks posed by specific juices and brands.

Arsenic in tube well water in Bangladesh: health and economic impacts and implications for arsenic mitigation.

A national drinking water quality survey conducted in 2009 furnished data that were used to make an updated estimate of chronic arsenic exposure in Bangladesh. About 20 million and 45 million people were found to be exposed to concentrations above the national standard of 50 µg/L and the World Health Organization's guideline value of 10 µg/L, respectively. From the updated exposure data and all-cause mortality hazard ratios based on local epidemiological studies, it was estimated that arsenic exposures to concentrations > 50 µg/L and 10-50 µg/L account for an annual 24,000 and perhaps as many as 19,000 adult deaths in the country, respectively. Exposure varies widely in the 64 districts; among adults, arsenic-related deaths account for 0-15% of all deaths. An arsenic-related mortality rate of 1 in every 16 adult deaths could represent an economic burden of 13 billion United States dollars (US$) in lost productivity alone over the next 20 years. Arsenic mitigation should follow a two-tiered approach: (i) prioritizing provision of safe water to an estimated 5 million people exposed to > 200 µg/L arsenic, and (ii) building local arsenic testing capacity. The effectiveness of such an approach was demonstrated during the United Nations Children's Fund 2006-2011 country programme, which provided safe water to arsenic-contaminated areas at a cost of US$ 11 per capita. National scale-up of such an approach would cost a few hundred million US dollars but would improve the health and productivity of the population, especially in future generations.

Environmental justice implications of arsenic contamination in California's San Joaquin Valley: a cross-sectional, cluster-design examining exposure and compliance in community drinking water systems.

BACKGROUND: Few studies of environmental justice examine inequities in drinking water contamination. Those studies that have done so usually analyze either disparities in exposure/harm or inequitable implementation of environmental policies. The US EPA's 2001 Revised Arsenic Rule, which tightened the drinking water standard for arsenic from 50 µg/L to 10 µg/L, offers an opportunity to analyze both aspects of environmental justice. METHODS: We hypothesized that Community Water Systems (CWSs) serving a higher proportion of minority residents or residents of lower socioeconomic status (SES) have higher drinking water arsenic levels and higher odds of non-compliance with the revised standard. Using water quality sampling data for arsenic and maximum contaminant level (MCL) violation data for 464 CWSs actively operating from 2005-2007 in California's San Joaquin Valley we ran bivariate tests and linear regression models. RESULTS: Higher home ownership rate was associated with lower arsenic levels (ß-coefficient= -0.27 µg As/L, 95% (CI), -0.5, -0.05). This relationship was stronger in smaller systems (ß-coefficient = -0.43, CI, -0.84, -0.03). CWSs with higher rates of homeownership had lower odds of receiving an MCL violation (OR, 0.33; 95% CI, 0.16, 0.67); those serving higher percentages of minorities had higher odds (OR, 2.6; 95% CI, 1.2, 5.4) of an MCL violation. CONCLUSIONS: We found that higher arsenic levels and higher odds of receiving an MCL violation were most common in CWSs serving predominantly socio-economically disadvantaged communities. Our findings suggest that communities with greater proportions of low SES residents not only face disproportionate arsenic exposures, but unequal MCL compliance challenges.

An updated inhalation unit risk factor for arsenic and inorganic arsenic compounds based on a combined analysis of epidemiology studies.

The United States Environmental Protection Agency (USEPA) developed an inhalation unit risk factor (URF) of 4.3E-03 per µg/m(3) for arsenic in 1984 for excess lung cancer mortality based on epidemiological studies of workers at two smelters: the Asarco smelter in Tacoma, Washington and the Anaconda smelter in Montana. Since the USEPA assessment, new studies have been published and exposure estimates were updated at the Asarco and Anaconda smelters and additional years of follow-up evaluated. The Texas Commission on Environmental Quality (TCEQ) has developed an inhalation URF for lung cancer mortality from exposures to arsenic and inorganic arsenic compounds based on a newer epidemiology study of Swedish workers and the updates of the Asarco and Anaconda epidemiology studies. Using a combined analysis approach, the TCEQ weighted the individual URFs from these three epidemiology cohort studies, to calculate a final inhalation URF of 1.5E-04 per µg/m(3). In addition, the TCEQ also conducted a sensitivity analysis, in which they calculated a URF based on a type of meta-analysis, and these results compared well with the results of the combined analysis. The no significant concentration level (i.e., air concentration at 1 in 100,000 excess lung cancer mortality) is 0.067µg/m(3). This value will be used to evaluate ambient air monitoring data so the general public in Texas is protected against adverse health effects from chronic exposure to arsenic.

Defining reference values of trace elements in the tear film: diagnostic methods and possible applications.

The study has been performed on tears of apparently healthy subjects who live and work in urban and rural areas, respectively. After the collection the following elements were investigated: chromium (Cr); arsenic (As); copper (Cu); zinc (Zn); selenium (Se); rubidium (Rb); barium (Ba); lead (Pb) and cobalt (Co). Significantly higher values of As were found in subjects living and working in rural areas as compared to those found in urban area residents (0.290 vs. 0.025; p<0.001). Conversely, Ba and Pb were significantly lower in rural area residents (1.10 vs. 2.50, p=0.027 and 1.70 vs. 1.10, p=0.057, respectively). Our data show that trace elements analysis in tears is possible; further studies could define if it could be a reliable biomarker in persons exposed to high concentration of trace elements due to working or environmental reasons.

Genotoxic potential of arsenic at its reference dose.

Arsenic, a highly hazardous contaminant in our drinking water, accounts for various toxic effects (including cancer) in human. However, intake of arsenic @0.3 µg kg(-1)day(-1) through drinking water, containing arsenic at its guideline value or maximum contaminant limit (10 µg L(-1)), has been estimated to pose very little or no measurable risk to cancer in humans. The value also appears to be equal to the human reference dose (or index dose) of arsenic based on human skin toxicity data. The present work was a quantitative assessment of the genotoxic potential of arsenic in mice at doses equivalent to its human reference dose as well as its multiples. Significant increases in the frequencies of chromosome abnormalities in the bone marrow cells were registered over the control level upon exposure to all the doses of arsenic including its reference dose (or index dose). The assessment of arsenic genotoxicity in humans at low doses will therefore be highly instrumental in establishing a permissible limit of arsenic in drinking water.