Charting achievements: a two-year retrospective of the society for environmental geochemistry and health (SEGH) and the evolving strategies.

Emerging from the shadow of the COVID-19 pandemic, it is time to ground ourselves and retrospectively assess the recent achievements of SEGH over the past years. This editorial serves as a comprehensive report on the progress made in comparison to the aspirations and goals set by the society's board in 2019 (Watts et al., Environ Geochem Health 42:343-347, 2019) (Fig. 1) and reflects on the state of the SEGH community as it reached its 50th anniversary at the close of 2021 (Watts et al. Environ Geochem Health 45:1165-1171, 2023). The focus lies on how the SEGH community navigated through the extraordinary challenges posed by the COVID-19 pandemic since early 2020, and to what extent the 2023 targets have been met.

Assessing the spatial distribution of elemental concentrations in surface sediments of Lake Victoria, Kenya: implications for ecological health and management.

Lacustrine sediment quality indicates the effects of both natural and anthropogenic activities on the ecosystem and communities. Despite its ecological importance, myriad complexities, and potential contaminant sources, the spatial distribution of surficial sediments in Lake Victoria's Winam Gulf has never been comprehensively documented. The purpose of this study was to assess the spatial distribution, pathways, and ecological risk of metal elements in the lake using a sediment matrix. Sediment samples were collected throughout the gulf in November 2022. The concentrations of Al, As, Cd, Co, Cr, Cu, Fe, K, Mn, Mo, Ni, P, Pb, Sb, Sn, Ti, Tl, U, and Zn were compared to different contamination metrics and ecological risk assessment indices. The average concentrations were in the following decreasing order: Zn > > > Cr > > Cu > Ni > Pb > Co > As > Cd with mean (± SD) of 185 ± 45 mg kg-1, 56 ± 15 mg kg-1, 45 ± 16 mg kg-1, 37 ± 11 mg kg-1, 24 ± 5 mg kg-1, 20 ± 7 mg kg-1, 3.9 ± 1.3 mg kg-1, 0.30 ± 0.09 mg kg-1, respectively, with strong indications of anthropogenic sources. Average concentrations were in the following decreasing order: Zn > > > Cr, Cu, Ni, Pb, Co, As, and Cd levels (mean ± SD) were 185 ± 45 mg kg-1, 56 ± 15 mg kg-1, 45 ± 16 mg kg-1, 37 ± 11 mg kg-1, 24 ± 5 mg kg-1, 20 ± 7 mg kg-1, 3.9 ± 1.3 mg kg-1 and 0.30 ± 0.09 mg kg-1 with strong indications of anthropogenic sources. The geo-accumulation index (Igeo) and enrichment factor categorisation schemes, respectively, classified these as uncontaminated (level 0) and depletion to minimal enrichment (level 1), while the ecological risk analysis classified them as "low risk". The mouth of the Nyando River, as well as Kisumu, Kendu, and Homa bays, were the most element-enriched and should be prioritised for focused monitoring and remediation. As a result, targeted land management of urban, industrial, transportation, and agricultural areas offers the opportunity to reduce sediment inputs into the lake ecosystem.

Considerations for environmental biogeochemistry and food security for aquaculture around Lake Victoria, Kenya.

The impact of population expansion through economic growth and development has been identified as one of the key drivers of both water and sediment contamination from potentially harmful elements (PHEs). This presents a major hazard not only to aquatic ecosystems but local riparian communities and beyond who rely heavily on this natural resource for drinking water and fish-a valuable source of dietary micronutrients and protein. The present study measured biogeochemical concentration of PHEs in water, sediment and fish from locations pooled into four zones within Winam Gulf and Lake Victoria area of Kenya. Captured fish were used as a sentinel receptor of lake health to evaluate potential risks to fisheries and aquaculture food security. In water, concentrations of arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu) and lead (Pb) were observed above the United States Environmental Protection Agency (US EPA) maximum contamination level drinking water guidelines (MCL), with aluminium (Al) observed above the Aquatic Life Criteria in all four zones. Similarly, sediment concentrations in all four zones exceeded the US EPA Effects range low (ERL) threshold guidelines for Cu, nickel (Ni), zinc (Zn) and Pb, with Cu, Zn and Pb classed at moderate contamination levels using the contamination factor. Fish tissue concentrations from the four zones were calculated using recommended daily intakes (RDI) and for PHEs as provisional maximum tolerable intakes (PMTIs) and indicated most macro- and micronutrients were at or below 10% RDI from aquaculture and wild fish, with Se indicating a greater RDI (16-29%) in all the zones. Contributions of PHEs to PMTIs were below threshold guidelines for both aquaculture and wild fish with only Cd, Cr and Pb levels being above the PMTI thresholds. There is a need to assess the long-term effects of persistent anthropogenic PHE input into Winam Gulf and the wider Lake Victoria basin. Continued monitoring of PHEs using both historical and more recent data will enable future management policies to be implemented through improved mitigation strategies to reduce their impact on water quality, fish health and subsequent human health.

Editorial: The society for environmental geochemistry and health (SEGH): 50 years and beyond.

When the SEGH international board released a short editorial paper back in 2019, we described an aim to increase the membership offering, whilst improving the diversity of input regionally, by scientific discipline and to ensure greater and more regular contact across the regions from 2020 onwards. Wider aspirations described in 2019 (Watts et al. 2019) are discussed within this short communication at the end of 2021 to evaluate progress made. In particular, how the SEGH community adapted to the unprecedented circumstances that have challenged each and every one of us throughout the COVID-19 pandemic since early 2020 and are likely to influence our activities for the foreseeable future.

Developments in Pb-210 methodologies to provide chronologies for environmental change.

Chronologies generated from core profiles to apply dates to environmental changes commonly use the measurement of the activity of radionuclides deposited and stratified with physical environmental material. The most commonly reported nuclide to define chronologies covering the last 150 years is Pb-210, for which accepted data processing methodologies in the literature have focussed on the constant rate of supply (CRS) model and the more recently published Bayesian Plum model. This short communication describes a validation approach using defined sediment layers referred to as 'varve' counting, which provide known points of reference to account for uncertainty between generated dates from each model using published Pb-210 measurements. A significant improvement in the chronologies was observed when applying reference date corrections to the models. This was shown to be essential in providing confidence in reported datasets and accuracy of predicted chronologies, which will better inform the interpretation of environmental change, e.g. sedimentation rates, climate change, pollution pathways and land degradation. Generated chronologies from both the CRS and Plum methods showed good agreement with the established varve dates (typically < 4-year difference).

Linking soils and human health: geospatial analysis of ground-sampled soil data in relation to community-level podoconiosis data in North West Cameroon.

BACKGROUND: Podoconiosis is a form of leg swelling, which arises when individuals are exposed over time to red clay soil formed from alkaline volcanic rock. The exact causal agent of the disease is unknown. This study investigates associations between podoconiosis disease data and ground-sampled soil data from North West Cameroon. METHODS: The mineralogy and elemental concentrations were measured in the soil samples and the data were spatially interpolated. Mean soil values were calculated from a 3 km buffer region around the prevalence data points to perform statistical analysis. Analysis included Spearman's rho correlation, binary logistic regression and principal component analysis (PCA). RESULTS: Six elements, barium, beryllium, potassium, rubidium, strontium and thallium, as well as two minerals, potassium feldspar and quartz, were identified as statistically related to podoconiosis. PCA did not show distinct separation between the spatial locations with or without recorded cases of podoconiosis, indicating that other factors such as shoe-wearing behaviour and genetics may significantly influence podoconiosis occurrence and prevalence in North West Cameroon. CONCLUSION: Several soil variables were statistically significantly related to podoconiosis. To further the current study, future investigations will look at the inflammatory pathway response of cells after exposure to these variables.

Elemental composition of aquaculture fish from West Bengal, India: nutrition versus food safety.

Aquaculture production continues to grow in West Bengal, where on average people consume 8.2 kg capita-1 of fish each year, and an extensive mosaic of aquaculture ponds has developed along the River Hugli as clay pits are repurposed. The adjacent brickworks and industry (especially tanneries) are a source of environmental pollution, with potential for bioaccumulation of potentially harmful elements (PHEs) in fish farmed in these ponds. Fish from aquaculture present an opportunity to meet food sufficiency in West Bengal; however, an investigation to assess their effectiveness for micronutrient supply balanced against food safety is required. Five ponds close to industrial brick manufacture (urban) and three from rural areas were assessed for the degree of pollution within their pond sediments and waters. Fish were also sampled from each location including a subset from the market in Kolkata to determine the concentrations of PHEs in their fish muscle tissue. Dietary intake and PHE loading were calculated for four fish species to evaluate their nutrient content with respect to recommended daily intakes for adults, e.g. calcium (Ca), potassium (K), magnesium (Mg), iron (Fe), zinc (Zn) and selenium (Se), and to establish whether the provisional maximum tolerable intakes (PMTIs) are exceeded for PHEs, e.g. aluminium (Al), arsenic (As), mercury (Hg), chromium (Cr), tin (Sn), copper (Cu) and lead (Pb). Preliminary results suggest that aquaculture is making an important contribution to nutrition, with fish being a good source of Se. However, in contrast to small wild-caught fish, aquaculture fish in the present study were poor sources of Fe, Ca and Zn. The fish also made substantial contributions (> 10%) to the PMTI of Hg and As. Therefore, there is an urgent need for ongoing monitoring and an expanded sampling programme, as well as research into approaches which might improve the nutritional quality of the farmed fish.

Investigating the use of microdialysis and SEC-UV-ICP-MS to assess iodine interactions in soil solution.

Element cycling in the terrestrial environment is heavily reliant upon processes that occur in soil solution. Here we present the first application of microdialysis to sample iodine from soil solution. In comparison to conventional soil solution extraction methods such as Rhizon™ samplers, centrifugation, and high-pressure squeezing, microdialysis can passively sample dissolved compounds from soil solution without altering the in-situ speciation of trace elements at realistic soil moisture conditions. In order to assess the suitability of microdialysis for sampling iodine, the permeability factors and effect of perfusion flowrate on I- and IO3- recovery was examined in stirred solutions. Furthermore, microdialysis was used to sample native soluble iodine at a range of water contents and iodine-enriched soils to investigate iodine soil dynamics. Total iodine concentrations were measured using ICP-MS. Inorganic species and the molecular weight distribution of organically bound iodine were determined by anion exchange and size exclusion chromatography (SEC) coupled to an ICP-MS, respectively. The most effective recovery rates in stirred solution were observed with the slowest perfusion flowrate yielding 66.2 ±â€¯7.1 and 70.5 ±â€¯7.1% for I- and IO3-, respectively. Microdialysis was proven to be capable of sampling dissolved iodine from the soil solution, which accounted for <2.5% of the total soil iodine and speciation followed the sequence: organic-I > I- > IO3-. The use of SEC coupled to (i) UV and (ii) ICP-MS analysis provided detail regarding the molecular weight distribution of dissolved org-I compounds. Dissolved org-I was detected with approximate molecular weights between 0.1 and 4.5 kDa. The results in this study show that microdialysis is a suitable technique for sampling dissolved iodine species from soils maintained at realistic moisture contents. In addition, inorganic iodine added to soils was predominately bound with relatively low molecular weight (<4.5 kDa) soluble organic matter.

Iodine uptake, storage and translocation mechanisms in spinach (Spinacia oleracea L.).

Iodine is an essential micronutrient for human health; phytofortification is a means of improving humans' nutritional iodine status. However, knowledge of iodine uptake and translocation in plants remains limited. In this paper, plant uptake mechanisms were assessed in short-term experiments (24 h) using labelled radioisotopes; the speciation of iodine present in apoplastic and symplastic root solutions was determined by (HPLC)-ICP-QQQ-MS. Iodine storage was investigated in spinach (Spinacia oleracea L.) treated with I- and IO3-. Finally, translocation through the phloem to younger leaves was also investigated using a radioiodine (129I-) label. During uptake, spinach roots demonstrated the ability to reduce IO3- to I-. Once absorbed, iodine was present as org-I or I- with significantly greater concentrations in the apoplast than the symplast. Plants were shown to absorb similar concentrations of iodine applied as I- or IO3-, via the roots, grown in an inert growth substrate. We found that whilst leaves were capable of absorbing radioactively labelled iodine applied to a single leaf, less than 2% was transferred through the phloem to younger leaves. In this paper, we show that iodine uptake is predominantly passive (approximately two-thirds of total uptake); however, I- can be absorbed actively through the symplast. Spinach leaves can absorb iodine via foliar fertilisation, but translocation is severely limited. As such, foliar application is unlikely to significantly increase the iodine content, via phloem translocation, of fruits, grains or tubers.

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.

Iodine soil dynamics and methods of measurement: a review.

Iodine is an essential micronutrient for human health: insufficient intake can have multiple effects on development and growth, affecting approximately 1.9 billion people worldwide. Previous reviews have focussed on iodine analysis in environmental and biological samples, however, no such review exists for the determination of iodine fractionation and speciation in soils. This article reviews the geodynamics of both stable 127I and the long-lived isotope 129I (t1/2 = 15.7 million years), alongside the analytical methods for determining iodine concentrations in soils, including consideration of sample preparation. The ability to measure total iodine concentration in soils has developed significantly from rudimentary spectrophotometric analysis methods to inductively coupled plasma mass spectrometry (ICP-MS). Analysis with ICP-MS has been reported as the best method for determining iodine concentrations in a range of environmental samples and soils due to developments in extraction procedures and sensitivity, with extremely good detection limits typically <µg L-1. The ability of ICP-MS to measure iodine and its capabilities to couple on-line separation tools has the significance to develop the understanding of iodine geodynamics. In addition, nuclear-related analysis and recent synchrotron light source analysis are discussed.

Source, distribution and ecotoxicological assessment of multielements in superficial sediments of a tropical turbid estuarine environment: A multivariate approach.

The work examined the distribution, possible sources and ecotoxicological assessment of 51 trace elements covering 13 sampling stations in surface sediments of coastal regions of Sundarban mangrove wetland and adjacent Hugli river estuary. The element concentrations exhibited an increasing trend towards downstream of the estuary (except lanthanides) with maximum enrichment for 22 elements at Gangadharpur (Sundarban region). According to Sediment Quality Guidelines (SQGs), the concentrations of Cu, As, Cr and Cd exceeded the Effects-Range-Low values, while Ni at certain stations exceeded the Effects-Range-Medium suggesting adverse effects on the sediment-dwelling organisms. The geoaccumulation index revealed that the stations were unpolluted to moderately polluted. Risk Index (357.61) and Enrichment factor (11.42) depicted that Nimtala station (upstream) was at high ecological risk zone. The result of PCA endorsed that organic carbon and clay fraction play crucial role in accumulating the elements in sediments. This pilot study contributes to a better understanding of the geochemistry of this complex deltaic ecosystem.

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-As(IMM), of urinary inorganic As species, arsenite (As(III)) and arsenate (As(V)), 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.

Iodine binding to humic acid.

The rate of reactions between humic acid (HA) and iodide (I(-)) and iodate (IO3(-)) have been investigated in suspensions spiked with (129)I at concentrations of 22, 44 and 88 µg L(-1) and stored at 10 °C. Changes in the speciation of (129)I(-), (129)IO3(-) and mixed ((129)I(-) + (129)IO3(-)) spikes were monitored over 77 days using liquid chromatography inductively coupled plasma mass spectrometry (LC-ICP-MS). In suspensions spiked with (129)I(-) 25% of the added I(-) was transformed into organic iodine (Org-(129)I) within 77 days and there was no evidence of (129)IO3(-) formation. By contrast, rapid loss of (129)IO3(-) and increase in both (129)I(-) and Org-(129)I was observed in (129)IO3(-)-spiked suspensions. However, the rate of Org-(129)I production was greater in mixed systems compared to (129)IO3(-)-spiked suspensions with the same total (129)I concentration, possibly indicating IO3(-)I(-) redox coupling. Size exclusion chromatography (SEC) demonstrated that Org-(129)I was present in both high and low molecular weight fractions of the HA although a slight preference to bond with the lower molecular weight fractions was observed indicating that, after 77 days, the spiked isotope had not fully mixed with the native (127)I pool. Iodine transformations were modelled using first order rate equations and fitted rate coefficients determined. However, extrapolation of the model to 250 days indicated that a pseudo-steady state would be attained after ∼200 days but that the proportion of (129)I incorporated into HA was less than that of (127)I indicating the presence of a recalcitrant pool of (127)I that was unavailable for isotopic mixing.

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.

Variability in the chemistry of private drinking water supplies and the impact of domestic treatment systems on water quality.

Tap water from 497 properties using private water supplies, in an area of metalliferous and arsenic mineralisation (Cornwall, UK), was measured to assess the extent of compliance with chemical drinking water quality standards, and how this is influenced by householder water treatment decisions. The proportion of analyses exceeding water quality standards were high, with 65 % of tap water samples exceeding one or more chemical standards. The highest exceedances for health-based standards were nitrate (11 %) and arsenic (5 %). Arsenic had a maximum observed concentration of 440 µg/L. Exceedances were also high for pH (47 %), manganese (12 %) and aluminium (7 %), for which standards are set primarily on aesthetic grounds. However, the highest observed concentrations of manganese and aluminium also exceeded relevant health-based guidelines. Significant reductions in concentrations of aluminium, cadmium, copper, lead and/or nickel were found in tap waters where households were successfully treating low-pH groundwaters, and similar adventitious results were found for arsenic and nickel where treatment was installed for iron and/or manganese removal, and successful treatment specifically to decrease tap water arsenic concentrations was observed at two properties where it was installed. However, 31 % of samples where pH treatment was reported had pH < 6.5 (the minimum value in the drinking water regulations), suggesting widespread problems with system maintenance. Other examples of ineffectual treatment are seen in failed responses post-treatment, including for nitrate. This demonstrates that even where the tap waters are considered to be treated, they may still fail one or more drinking water quality standards. We find that the degree of drinking water standard exceedances warrant further work to understand environmental controls and the location of high concentrations. We also found that residents were more willing to accept drinking water with high metal (iron and manganese) concentrations than international guidelines assume. These findings point to the need for regulators to reinforce the guidance on drinking water quality standards to private water supply users, and the benefits to long-term health of complying with these, even in areas where treated mains water is widely available.

Iodine source apportionment in the Malawian diet.

The aim of this study was to characterise nutritional-I status in Malawi. Dietary-I intakes were assessed using new datasets of crop, fish, salt and water-I concentrations, while I status was assessed for 60 women living on each of calcareous and non-calcareous soils as defined by urinary iodine concentration (UIC). Iodine concentration in staple foods was low, with median concentrations of 0.01 mg kg(-1) in maize grain, 0.008 mg kg(-1) in roots and tubers, but 0.155 mg kg(-1) in leafy vegetables. Freshwater fish is a good source of dietary-I with a median concentration of 0.51 mg kg(-1). Mean Malawian dietary-Iodine intake from food, excluding salt, was just 7.8 µg d(-1) compared to an adult requirement of 150 µg d(-1). Despite low dietary-I intake from food, median UICs were 203 µg L(-1) with only 12% defined as I deficient whilst 21% exhibited excessive I intake. Iodised salt is likely to be the main source of dietary I intake in Malawi; thus, I nutrition mainly depends on the usage and concentration of I in iodised salt. Drinking water could be a significant source of I in some areas, providing up to 108 µg d(-1) based on consumption of 2 L d(-1).

Arsenic speciation in polychaetes (Annelida) and sediments from the intertidal mudflat of Sundarban mangrove wetland, India.

This paper documents the concentration of total arsenic and individual arsenic species in four soft-bottom benthic polychaetes (Perenereis cultifera, Ganganereis sootai, Lumbrinereis notocirrata and Dendronereis arborifera) along with host sediments from Sundarban mangrove wetland, India. An additional six sites were considered exclusively for surface sediments for this purpose. Polychaetes were collected along with the host sediments and measured for their total arsenic content using inductively coupled plasma mass spectrometry. Arsenic concentrations in polychaete body tissues varied greatly, suggesting species-specific characteristics and inherent peculiarities in arsenic metabolism. Arsenic was generally present in polychaetes as arsenate (As(V) ranges from 0.16 to 0.50 mg kg(-1)) or arsenite (As(III) ranges from 0.10 to 0.41 mg kg(-1)) (30-53 % as inorganic As) and dimethylarsinic acid (DMA(V) <1-25 %). Arsenobetaine (AB < 16 %), and PO(4)-arsenoriboside (8-48 %) were also detected as minor constituents, whilst monomethylarsonic acid (MA(V)) was not detected in any of the polychaetes. The highest total As (14.7 mg kg(-1) dry wt) was observed in the polychaete D. arborifera collected from the vicinity of a sewage outfall in which the majority of As was present as an uncharacterised compound (10.3 mg kg(-1) dry wt) eluted prior to AB. Host sediments ranged from 2.5 to 10.4 mg kg(-1) of total As. This work supports the importance of speciation analysis of As, because of the ubiquitous occurrence of this metalloid in the environment, and its variable toxicity depending on chemical form. It is also the first work to report the composition of As species in polychaetes from the Indian Sundarban wetlands.

Arsenic contamination of natural waters in San Juan and La Pampa, Argentina.

Arsenic (As) speciation in surface and groundwater from two provinces in Argentina (San Juan and La Pampa) was investigated using solid phase extraction (SPE) cartridge methodology with comparison to total arsenic concentrations. A third province, Río Negro, was used as a control to the study. Strong cation exchange (SCX) and strong anion exchange (SAX) cartridges were utilised in series for the separation and preservation of arsenite (As(III)), arsenate (As(V)), monomethylarsonic acid (MA(V)) and dimethylarsinic acid (DMA(V)). Samples were collected from a range of water outlets (rivers/streams, wells, untreated domestic taps, well water treatment works) to assess the relationship between total arsenic and arsenic species, water type and water parameters (pH, conductivity and total dissolved solids, TDS). Analysis of the waters for arsenic (total and species) was performed by inductively coupled plasma mass spectrometry (ICP-MS) in collision cell mode. Total arsenic concentrations in the surface and groundwater from Encon and the San José de Jáchal region of San Juan (north-west Argentina within the Cuyo region) ranged from 9 to 357 µg l(-1) As. Groundwater from Eduardo Castex (EC) and Ingeniero Luiggi (LU) in La Pampa (central Argentina within the Chaco-Pampean Plain) ranged from 3 to 1326 µg l(-1) As. The pH range for the provinces of San Juan (7.2-9.7) and La Pampa (7.0-9.9) are in agreement with other published literature. The highest total arsenic concentrations were found in La Pampa well waters (both rural farms and pre-treated urban sources), particularly where there was high pH (typically > 8.2), conductivity (>2,600 µS cm(-1)) and TDS (>1,400 mg l(-1)). Reverse osmosis (RO) treatment of well waters in La Pampa for domestic drinking water in EC and LU significantly reduced total arsenic concentrations from a range of 216-224 µg l(-1) As to 0.3-0.8 µg l(-1) As. Arsenic species for both provinces were predominantly As(III) and As(V). As(III) and As(V) concentrations in San Juan ranged from 4-138 µg l(-1) to <0.02-22 µg l(-1) for surface waters (in the San José de Jáchal region) and 23-346 µg l(-1) and 0.04-76 µg l(-1) for groundwater, respectively. This translates to a relative As(III) abundance of 69-100% of the total arsenic in surface waters and 32-100% in groundwater. This is unexpected because it is typically thought that in oxidising conditions (surface waters), the dominant arsenic species is As(V). However, data from the SPE methodology suggests that As(III) is the prevalent species in San Juan, indicating a greater influence from reductive processes. La Pampa groundwater had As(III) and As(V) concentrations of 5-1,332 µg l(-1) and 0.09-592 µg l(-1) for EC and 32-242 µg l(-1) and 30-277 µg l(-1) As for LU, respectively. Detectable levels of MA(V) were reported in both provinces up to a concentration of 79 µg l(-1) (equating to up to 33% of the total arsenic). Previously published literature has focused primarily on the inorganic arsenic species, however this study highlights the potentially significant concentrations of organoarsenicals present in natural waters. The potential for separating and preserving individual arsenic species in the field to avoid transformation during transport to the laboratory, enabling an accurate assessment of in situ arsenic speciation in water supplies is discussed.