Urinary arsenic profiles reveal exposures to inorganic arsenic from private drinking water supplies in Cornwall, UK

Private water supplies (PWS) in Cornwall, South West England exceeded the current WHO guidance value and UK prescribed concentration or value (PCV) for arsenic of 10 μg/L in 5% of properties surveyed (n = 497). In this follow-up study, the first of its kind in the UK, volunteers (n = 207) from 127 households who used their PWS for drinking, provided urine and drinking water samples for total As determination by inductively coupled plasma mass spectrometry (ICP-MS) and urinary As speciation by high performance liquid chromatography ICP-MS (HPLC-ICP-MS). Arsenic concentrations exceeding 10 μg/L were found in the PWS of 10% of the volunteers. Unadjusted total urinary As concentrations were poorly correlated (Spearman’s ρ = 0.36 (P < 0.001)) with PWS As largely due to the use of spot urine samples and the dominance of arsenobetaine (AB) from seafood sources. However, the osmolality adjusted sum, U-AsIMM, of urinary inorganic As species, arsenite (AsIII) and arsenate (AsV), and their metabolites, methylarsonate (MA) and dimethylarsinate (DMA), was found to strongly correlate (Spearman’s ρ: 0.62 (P < 0.001)) with PWS As, indicating private water supplies as the dominant source of inorganic As exposure in the study population of PWS users

Surface wipe and bulk sampling of household dust: arsenic exposure in Cornwall, UK

Dust elemental levels can be expressed as concentrations (bulk samples) or surface loadings (wipe samples). Wipe sampling has not been widely adopted for elements other than lead (Pb). In this study, 433 wipe samples from 130 households in south west England – a region of widespread, natural and anthropogenic arsenic contamination linked with previous mining activities-were analysed to (i) quantify loadings of arsenic (As); (ii) assess the quality of wipe data using QA/QC criteria; (iii) estimate, using published ingestion rates, human exposure to As in dust using loadings and concentrations from 97 bulk samples and (iv) comparatively assess the performance of wipe and bulk sampling using associations with As biomonitoring data (urine, toenails and hair). Good QC performance was observed for wipes: strong agreement between field duplicates, non-detectable contamination of field blank wipes and good reference material recoveries. Arsenic loadings exceeded an existing urban background benchmark in 67 (52%) households. No exceedances of tolerable daily As intake were observed for adult exposure estimates but infant estimates exceeded for 1 household. Infant estimates calculated using bulk concentrations resulted in 4 (3%) exceedances. Neither wipe nor bulk As metrics were sufficiently better predictors of As in biospecimens. Sampling strategies, analytical protocols, exposure metrics and assessment criteria require refinement to validate dust sampling methodologies

Prolonged exposure to arsenic in UK private water supplies: toenail, hair and drinking water concentrations

Chronic exposure to arsenic (As) in drinking water is an established cause of cancer and other adverse health effects. Arsenic concentrations >10 μg L−1 were previously measured in 5% of private water supplies (PWS) in Cornwall, UK. The present study investigated prolongued exposure to As by measuring biomarkers in hair and toenail samples from 212 volunteers and repeated measurements of As in drinking water from 127 households served by PWS. Strong positive Pearson correlations (rp = 0.95) indicated stability of water As concentrations over the time period investigated (up to 31 months). Drinking water As concentrations were positively correlated with toenail (rp = 0.53) and hair (rp = 0.38) As concentrations – indicative of prolonged exposure. Analysis of washing procedure solutions provided strong evidence of the effective removal of exogenous As from toenail samples. Significantly higher As concentrations were measured in hair samples from males and smokers and As concentrations in toenails were negatively associated with age. A positive association between seafood consumption and toenail As and a negative association between home-grown vegetable consumption and hair As was observed for volunteers exposed to <1 As μg L−1 in drinking water. These findings have important implications regarding the interpretation of toenail and hair biomarkers. Substantial variation in biomarker As concentrations remained unaccounted for, with soil and dust exposure as possible explanations

Evolution and paragenetic context of low delta D hydrothermal fluids from the Panasqueira W-Sn deposit, Portugal: New evidence from microthermometric, stable isotope, noble gas and halogen analyses of primary fluid inclusions

The evolution, paragenetic context and origin of remarkably low delta D hydrothermal fluids from the Hercynian Panasqueira W- Sn-Cu(Ag) deposit have been investigated through a combined microthermometric, stable isotope, halogen and noble gas fluid inclusion study. Large variations in delta D between -60 parts per thousand and -134 parts per thousand have been observed in primary fluid inclusions from growth zones in a quartz crystal (Pa66) paragenetically constrained to the main sulfide stage (MSS) of ore formation. The same fluids exhibited relatively constant fluid inclusion homogenisation temperatures (254 to 260 degrees C), salinities (7.4 to 8.7 wt.% NaCl equivalent) and calculated fluid delta(18)O (3.8 to 4.4 parts per thousand). All the fluids exhibited Ar-40 excesses. Mean molar Br/Cl and I/Cl ratios varied from 2.3 x 10(-3)-4.2 x 10(-3) and 8 x 10(-4)-10 x 10(-4) respectively, with the more Br-rich fluids being associated with the more deuterium-depleted fluids. The low palaeolatitude of Panasqueira throughout the main stages of ore formation and the overwhelming predominance of meteoric fluids in the main, late and post-ore mineralising fluids with delta D of -40 to -65 parts per thousand lends little support for any models involving low delta D palaeometeoric water. The limited range of Ar-40*/Cl ratios (1.1 x 10(-5)-1.6 x 10(-5)) also precludes boiling during the MSS or mixing of meteoric water with highly fractionated deuterium-depleted magmatic waters as viable mechanisms for producing the low delta D fluids. The high Br/Cl and I/Cl of the MSS fluids indicate significant fluid interactions with organic rich sediments or metasediments, in particular regionally abundant Carboniferous coals or coaly sediments that are inferred to be depleted in deuterium by around 85 parts per thousand compared to palaeometeoric water. The large range of delta D observed in the MSS fluids may be explained by isotopic exchange of palaeometeoric water with these coals at varying water/rock (wt./wt.) ratios between 0.02 and 0.002 with fluid oxygen isotopic compositions controlled by exchange with the Beira Schists. Such a model is consistent with the requirements that any satisfactory model must take into account viz. (i) the relative constancy of temperature, salinity, Ar-40* and fluid delta(18)O during excursions to low delta D; (ii) the high I/Cl and Br/Cl ratios observed; and (iii) the coincidence of these low delta D fluids with the onset of precipitation of polymetallic sulfides and phosphates under reducing conditions. The model indicates that (meta)sedimentary sources of ore forming components became increasingly important during the evolution of the Panasqueira Sn-W deposit and accounts in part for the observed progression from oxide-dominated to base-metal sulfide-dominated parageneses

Hopane, sterane and n-alkane distributioons in shallow sediments hosting high arsenic groundwaters in Cambodia

The presence of elevated As in ground waters exploited for drinking water and irrigation in South-East Asia is causing serious impacts on human health. A key mechanism that causes the mobilization of As in these waters is microbially mediated reductive transformation of As-bearing Fe(III) hydrated oxides and the role of degradable organic matter (OM) in this process is widely recognized. A number of different types of OM that drive As release in these aquifers have been suggested, including petroleum derived hydrocarbons naturally seeping into shallow sediments from deeper thermally mature source rocks. However, the amount of information on the characteristics of the OM in South-East Asian aquifers is limited. Here the organic geochemical analyses of the saturated hydrocarbon fractions and radiocarbon analysis, of two additional sites in SE Asia are reported. The results show that the OM in a given sedimentary horizon likely derives from multiple sources including naturally occurring petroleum. The importance of naturally occurring petroleum as one of the sources was clearly indicated by the n-alkane CPI of approximately 1, the presence of an unresolved complex mixture, and hopane (dominated by 17α(H),21β(H) hopanes) and sterane distribution patterns. The results also indicate that the OM in these aquifers varies tremendously in content, character and potential bioavailability. Furthermore, the presence of petroleum derived OM in sediments at both sites doubles the number of locations where their presence has been observed in association with As-rich, shallow aquifers, suggesting that the role of petroleum derived OM in microbially mediated As release might occur over a wider range of geographical locations than previously thought