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.

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.

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.

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.

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.

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.

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.

Evaluation of radiochemical neutron activation analysis methods for determination of arsenic in biological materials.

Radiochemical neutron activation analysis (RNAA) with retention on hydrated manganese dioxide (HMD) has played a key role in the certification of As in biological materials at NIST. Although this method provides very high and reproducible yields and detection limits at low microgram/kilogram levels, counting geometry uncertainties may arise from unequal distribution of As in the HMD, and arsenic detection limits may not be optimal due to significant retention of other elements. An alternate RNAA procedure with separation of arsenic by solvent extraction has been investigated. After digestion of samples in nitric and perchloric acids, As(III) is extracted from 2 M sulfuric acid solution into a solution of zinc diethyldithiocarbamate in chloroform. Counting of (76)As allows quantitation of arsenic. Addition of an (77)As tracer solution prior to dissolution allows correction for chemical yield and counting geometries, further improving reproducibility. The HMD and solvent extraction procedures for arsenic were compared through analysis of SRMs 1577c (bovine liver), 1547 (peach leaves), and 1575a (pine needles). Both methods gave As results in agreement with certified values with comparable reproducibility. However, the solvent extraction method yields a factor of 3 improvement in detection limits and is less time-consuming than the HMD method. The new method shows great promise for use in As certification in reference materials.

Arsenic in freshwater fish in the Chihuahua County water reservoirs (Mexico).

Water reservoirs in Chihuahua County, Mexico, are affected by some punctual and non-punctual geogenic and anthropogenic pollution sources; fish are located at the top of the food chain and are good indicators for the ecosystems pollution. The study goal was to: (i) determine arsenic concentration in fish collected from the Chuviscar, Chihuahua, San Marcos and El Rejon water reservoirs; (ii) to assess if the fishes are suitable for human consumption and (iii) link the arsenic contents in fish with those in sediment and water reported in studies made the same year for these water reservoirs. Sampling was done in summer, fall and winter. The highest arsenic concentration in the species varied through the sampling periods: Channel catfish (Ictalurus punctatus) with 0.22 ± 0.15 mg/kg dw in winter and Green sunfish (Lepomis cyanellus) with 2.00 ± 0.15 mg/kg dw in summer in El Rejon water reservoir. A positive correlation of arsenic contents was found through all sampling seasons in fish samples and the samples of sediment and water. The contribution of the weekly intake of inorganic arsenic, based on the consumption of 0.245 kg fish muscles/body weight/week was found lower than the acceptable weekly intake of 0.015 mg/kg/body weight for inorganic arsenic suggested by FAO/WHO.

Natural contamination with arsenic and other trace elements in groundwater of the Central-West region of Chaco, Argentina.

This study covered the central agricultural region of the Chaco province, which lacks a permanent river networks. However, during the rainy period there is localized groundwater recharge. About 84 groundwater samples were taken during the period April-December 2007. These groundwater samples were collected from two different depths: 62 samples from shallow wells (4 to 20 m) and 24 samples from deep wells (20 to 100 m). Chemical variables were determined: pH, specific conductance, total dissolved solid, hardness, alkalinity, HCO(3)-, CO(3)(2-), SO(4)(2-), Cl-, NO(3)-, NO(2) -, NH(4)+, F-, As((tot)), Na+, K+, Ca2+, Mg2+, Fe, Cu, Ni, Pb and Zn. The chemical composition of groundwater in the study area is dominantly sodium bicarbonate and sodium chloride bicarbonate, comprising more than 60% (52/86) of shallow and deep groundwater samples. Of the 86 analyzed groundwater samples, 88% exceeded the WHO (World Health Organization) and CAA (Código Alimentario Argentino) standards (10 µg/L) for As (arsenic) and 9% exceeded the WHO standard (1.5 mg/L) for F(-).Groundwater highly contaminated with As (max. 1,073 µg/L) and F- (max. 4.2 mg/L) was found in shallow aquifer. The contaminated groundwater is characterized by high pH (max. 8.9), alkalinity (max. HCO(3)- 1,932 mg/L), SO(4)(2-) (max. 11,862 mg/L), Na(+) (max. 3,158 mg/L), Cl(-) (max. 10,493 mg/L) and electric conductivity greater than 33.3 µS/cm. Other associated elements (Ni, Pb, Cu and Zn) are present in low concentrations, except for Fe that in 32% of samples exceeded the guideline value of 0.3 mg/L suggested by the CAA.

The electrocoagulation/advanced oxidation treatment of the groundwater used for human consumption.

The purpose of this work was development and application of the purification system suitable for the treatment of groundwater used for human consumption, satisfying following criteria: (a) no need for external addition of the chemicals; (b) simultaneous removal of wide range of contaminants present in the treated water; (c) low sensitivity to the changes in the composition of the treated water; (d) high quality of treated water with regards to all measured parameters. Therefore the well water from the 60 m deep water layer situated near the city of Osijek (Eastern Croatia) with elevated values of heavy metals, color, turbidity, suspended solids, ammonia and organic contaminants was processed. Due to the complex composition of the treated water, the purification system required the combination of electroreduction/electrocoagulation, using iron and aluminum electrode plates followed by the simultaneous ozonation/UV treatment. The electroreduction/electrocoagulation approach was used for the removal of heavy metals, suspended solids, color and turbidity, while the organic contaminants and ammonia were removed by the ozonation/UV treatment. All measured parameters in the purified water were significantly lower compared to the regulated values. Under the optimum treatment conditions, the removal efficiencies for color, turbidity, nickel and arsenic were 100%. The removal efficiencies of V, Cr, Mn, Fe, Cu, Zn, Pb, ammonia, fluorides, sulfates and COD were 94.5%, 96.0%, 98.3%, 99.6%, 99.7%, 97.8%, 96.7%, 96,7%, 93.4%, 51.4%, 72.2% and 93.8%, respectively, increasing with the increased initial concentrations.

A comprehensive review of arsenic levels in the semiconductor manufacturing industry.

This paper presents a summary of arsenic level statistics from air and wipe samples taken from studies conducted in fabrication operations. The main objectives of this study were not only to describe arsenic measurement data but also, through a literature review, to categorize fabrication workers in accordance with observed arsenic levels. All airborne arsenic measurements reported were included in the summary statistics for analysis of the measurement data. The arithmetic mean was estimated assuming a lognormal distribution from the geometric mean and the geometric standard deviation or the range. In addition, weighted arithmetic means (WAMs) were calculated based on the number of measurements reported for each mean. Analysis of variance (ANOVA) was employed to compare arsenic levels classified according to several categories such as the year, sampling type, location sampled, operation type, and cleaning technique. Nine papers were found reporting airborne arsenic measurement data from maintenance workers or maintenance areas in semiconductor chip-making plants. A total of 40 statistical summaries from seven articles were identified that represented a total of 423 airborne arsenic measurements. Arsenic exposure levels taken during normal operating activities in implantation operations (WAM = 1.6 µg m⁻³, no. of samples = 77, no. of statistical summaries = 2) were found to be lower than exposure levels of engineers who were involved in maintenance works (7.7 µg m⁻³, no. of samples = 181, no. of statistical summaries = 19). The highest level (WAM = 218.6 µg m⁻³) was associated with various maintenance works performed inside an ion implantation chamber. ANOVA revealed no significant differences in the WAM arsenic levels among the categorizations based on operation and sampling characteristics. Arsenic levels (56.4 µg m⁻³) recorded during maintenance works performed in dry conditions were found to be much higher than those from maintenance works in wet conditions (0.6 µg m⁻³). Arsenic levels from wipe samples in process areas after maintenance activities ranged from non-detectable to 146 µg cm⁻², indicating the potential for dispersion into the air and hence inhalation. We conclude that workers who are regularly or occasionally involved in maintenance work have higher potential for occupational exposure than other employees who are in charge of routine production work. In addition, fabrication workers can be classified into two groups based on the reviewed arsenic exposure levels: operators with potential for low levels of exposure and maintenance engineers with high levels of exposure. These classifications could be used as a basis for a qualitative ordinal ranking of exposure in an epidemiological study.

Biomonitoring equivalents for inorganic arsenic.

This paper presents Biomonitoring Equivalents (BEs) for inorganic arsenic. Biomonitoring Equivalents (BEs) are defined as the concentration or range of concentrations of a chemical or its metabolite in a biological medium (blood, urine, or other medium) that is consistent with an existing health-based exposure guideline, and are derived by integrating available data on pharmacokinetics with existing chemical risk assessments. This study reviews available health-based exposure guidance values for arsenic based on recent evaluations from the United States Environmental Protection Agency (US EPA), US Agency for Toxic Substances and Disease Registry (ATSDR) and Health Canada (HC). BE values corresponding to the Reference Dose (RfD) or risk-specific doses for cancer endpoints from these agencies were derived based on kinetic data (urinary excretion) from controlled dosing studies in humans. The BE values presented here provide estimates of the sum of inorganic arsenic-derived urinary biomarkers (inorganic arsenic, monomethylated arsenic, and dimethylated arsenic). The BE associated with the United States Environmental Protection Agency's Reference Dose and the Agency for Toxic Substances and Disease Registry's Minimal Risk Level is 6.4 microg arsenic/L urine. The BEs associated with the various cancer risk assessments are significantly lower. These BE values may be used as screening tools for evaluation of biomonitoring data for inorganic arsenic in a public health risk context.

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.

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.

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.