Arsenic and Other Metal Contamination of Groundwaters in the Industrial Area of Thessaloniki, Northern Greece

In groundwater, used for drinking water supply in the greater industrial area of Thessaloniki, in Northern Greece, concentrations of total arsenic exceeded the WHO provisional guideline value and the EU maximum contaminant level (MCL) of 10 μg/L. The concentration of total arsenic was in the range between 4–130 μg/L, whereas the median value was 36 μg/L and the average concentration 46 μg/L. Nine out of the eleven wells contained total arsenic at concentration higher than 10 μg/L and it should be stressed that 6 of them contain arsenic at concentrations between 10 (new MCL) and 50 μg/L (previous MCL). The examined groundwaters were found to contain elevated concentrations of manganese and phosphate. Arsenic had a positive correlation with the pH, indicating the possible effect of pH on arsenic mobilisation. These findings emerge the problem of contamination from arsenic, since, according to the EU directive 98/83, all drinking water sources within the European Union should have achieved compliance with the new limits by 12/2003, implying that the situation requires urgent remedial action.     

Arsenic concentration variability, health risk assessment, and source identification using multivariate analysis in selected villages of public water system, Lahore, Pakistan

This paper reports high levels and variability in arsenic (As) levels at locations identified as one of the highest As-contaminated locations in Pakistan. Groundwater pollution related to arsenic has been reported since many years in the areas lying in outskirts of District Lahore, Pakistan. A comparative study is done to determine temporal variations of As from three villages, i.e., Kalalanwala (KLW), Manga Mandi (MM), and Shamki Bhattian (SKB). Seventy-three percent of the 30 investigated samples ranging in depth from 20 to 200 m, show an increasing trend in variations of As concentration over a time span of 4 years and 87 % of samples exceeded the WHO standard of 10 μg/L for As while 77 % of samples have As concentration >50 μg/L (national standard). Further results indicate that high levels of As is accompanied with increase pH (r?=?0.8) favoring desorption of As from minerals at higher pH under oxidizing conditions. For health risk assessment of arsenic, the average daily dose, hazard quotient (HQ), and cancer risk were calculated. The residents of the studied areas had toxic risk index in the order of SKB>KLW>MM, with 87 % of samples exceeding the typical toxic risk index 1.00 (ranging from 2.3–48.6) which was 83 % (ranging from 0.3–41) 4 years before. The results of the present study therefore indicate that arsenic concentrations are increasing in the area, which needs an immediate attention to provide alternate sources of water to save people at risk.     

Arsenic occurrence and accumulation in soil and water of eastern districts of Uttar Pradesh, India

Arsenic in the soil and water of eastern districts of Uttar Pradesh (Ballia and Ghazipur) was estimated. Survey results revealed that arsenic in soil samples ranged from 5.40 to 15.43 parts per million (ppm). In water samples, it ranged from 43.75 to 620.75 parts per billion (ppb) which far exceeded the permissible limit of 10 ppb as recommended by the World Health Organization. Maximum concentration of arsenic in water was found in Haldi village of Ballia (620.75 ppb). However, mean arsenic concentration in water followed the order: Karkatpur (257.21 ppb) < Haldi (310.15 ppb) < Sohaon (346.94 ppb) < Dharmarpur (401.75 ppb). In case of soil, maximum arsenic was detected in soil of Sohaon (15.43 ppm). Mean arsenic levels in soils followed the order: Karkatpur (9.24 ppm) < Haldi (9.82 ppm) < Dharmarpur (11.32 ppm) < Sohaon (14.08 ppm). Arsenic levels were higher in soils collected from 15–30 cm depth than 0–15 cm from the soil surface.     

Arsenic exposure in Hungary, Romania and Slovakia

Inorganic arsenic is a potent human carcinogen and toxicant which people are exposed to mainly via drinking water and food. The objective of the present study was to assess current exposure to arsenic via drinking water in three European countries. For this purpose, 520 individuals from four Hungarian, two Slovakian and two Romanian countries were investigated by measuring inorganic arsenic and methylated arsenic metabolites in urine by high performance liquid chromatography with hydride generation and inductively coupled plasma mass spectrometry. Arsenic in drinking water was determined by atomic absorption spectrometry. Significantly higher concentrations of arsenic were found in both the water and the urine samples from the Hungarian counties (median: 11 and 15 microg dm(-3), respectively; p < 0.001) than from the Slovakian (median: 0.94 and 4.5 microg dm(-3), respectively) and Romanian (median: 0.70 and 2.1 microg dm(-3), respectively) counties. A significant correlation was seen between arsenic in water and arsenic in urine (R(2)= 0.46). At low water arsenic concentrations, the relative amount of dimethylarsinic acid (DMA) in urine was increased, indicating exposure via food. Also, high body mass index was associated with higher concentrations of arsenic in urine (p= 0.03), mostly in the form of DMA. Smokers had significantly higher urinary arsenic concentrations than non-smokers (p= 0.03). In conclusion, elevated arsenic exposure via drinking water was prevalent in some of the counties. Exposure to arsenic from food, mainly as DMA, and cigarette smoke, mainly as inorganic arsenic, are major determinants of arsenic exposure at very low concentrations of arsenic in drinking water.     

Co-occurrence profiles of trace elements in potable water systems: a case study

Potable water samples (N?=?74) from 19 zip code locations in a region of Greece were profiled for 13 trace elements composition using inductively coupled plasma mass spectrometry. The primary objective was to monitor the drinking water quality, while the primary focus was to find novel associations in trace elements occurrence that may further shed light on common links in their occurrence and fate in the pipe scales and corrosion products observed in urban drinking water distribution systems. Except for arsenic at two locations and in six samples, rest of the analyzed elements was below maximum contaminant levels, for which regulatory values are available. Further, we attempted to hierarchically cluster trace elements based on their covariances resulting in two groups; one with arsenic, antimony, zinc, cadmium, and copper and the second with the rest of the elements. The grouping trends were partially explained by elements’ similar chemical activities in water, underscoring their potential for co-accumulation and co-mobilization phenomena from pipe scales into finished water. Profiling patterns of trace elements in finished water could be indicative of their load on pipe scales and corrosion products, with a corresponding risk of episodic contaminant release. Speculation was made on the role of disinfectants and disinfection byproducts in mobilizing chemically similar trace elements of human health interest from pipe scales to tap water. It is warranted that further studies may eventually prove useful to water regulators from incorporating the acquired knowledge in the drinking water safety plans.     

UV/H2O2 oxidation of arsenic and terbuthylazine in drinking water

Arsenic is a widespread contaminant in the environment. The intake of water containing high concentrations of arsenic could have serious impact on human health, such as skin and lung cancer. In the European Union, thus, also in Italy, the arsenic limit in drinking water is 10 μg L^?1. Several water remediation treatment technologies are available for arsenic removal. For some processes, the removal efficiencies can be improved after an oxidation step. Most full-scale applications are based on conventional oxidation processes for chemical micropollutant removal. However, if water contains arsenic and refractory organic contaminants, the advanced oxidation processes could be considered. The aim of this work was to investigate the effectiveness of ultraviolet (UV) radiation alone and in combination with hydrogen peroxide for the oxidation of arsenic and terbuthylazine (TBA). The experimental tests were performed in groundwater at the laboratory scale (0.1 mg L^?1 As(III) and 10 μg L^?1 TBA). Hydrogen peroxide alone (15 mg L^?1) was ineffective on both arsenic and TBA oxidation; the 253.7-nm radiation alone did not oxidize arsenic(III), but photolyzed efficiently TBA (52 % removal yield at a UV dose of 1,200 mJ cm^?2). The UV/H₂O₂ advanced oxidation (UV dose 600–2,000 mJ cm^?2, 5–15 mg L^?1 H₂O₂) was the most effective process for the oxidation of both arsenic and TBA, with observed oxidation efficiencies of 85 and 94 %, respectively, with 5 mg L^?1 H₂O₂ and a UV dose of 2,000 mJ cm^?2.     

Using a relative health indicator (RHI) metric to estimate health risk reductions in drinking water

When a new drinking water regulation is being developed, the USEPA conducts a health risk reduction and cost analysis to, in part, estimate quantifiable and non-quantifiable cost and benefits of the various regulatory alternatives. Numerous methodologies are available for cumulative risk assessment ranging from primarily qualitative to primarily quantitative. This research developed a summary metric of relative cumulative health impacts resulting from drinking water, the relative health indicator (RHI). An intermediate level of quantification and modeling was chosen, one which retains the concept of an aggregated metric of public health impact and hence allows for comparisons to be made across “cups of water,” but avoids the need for development and use of complex models that are beyond the existing state of the science. Using the USEPA Six-Year Review data and available national occurrence surveys of drinking water contaminants, the metric is used to test risk reduction as it pertains to the implementation of the arsenic and uranium maximum contaminant levels and quantify “meaningful” risk reduction. Uranium represented the threshold risk reduction against which national non-compliance risk reduction was compared for arsenic, nitrate, and radium. Arsenic non-compliance is most significant and efforts focused on bringing those non-compliant utilities into compliance with the 10 μg/L maximum contaminant level would meet the threshold for meaningful risk reduction.     

Urinary 8-hydroxy-2'-deoxyguanosine in inhabitants chronically exposed to arsenic in groundwater in Cambodia

Arsenic concentrations in hair and urine, and urinary levels of 8-hydroxy-2'-deoxyguanosine (8-OHdG), a marker of oxidative DNA damage, were examined for inhabitants of the Mekong Basin in Kratie Province, Cambodia. Also, the arsenic levels of tube-well water were determined. Total arsenic concentrations in tube-well water ranged from <1 to 886 microg L(-1), and 44.8% of these exceeded the WHO drinking water guideline of 10 microg L(-1). Elevated levels of arsenic were observed in the human hair and urine, and also a significant positive correlation was observed between the concentrations in hair and urine. These results suggest that the inhabitants are chronically exposed to arsenic through drinking the tube-well water. Levels of urinary 8-OHdG were higher for the subjects with higher arsenic levels in hair and urine, suggesting that induction of oxidative DNA damage was caused by chronic exposure to arsenic in tube-well water for the inhabitants in Kratie Province. To our knowledge, this is the first report on the oxidative DNA damage caused by chronic exposure to arsenic in groundwater for the inhabitants in Cambodia.     

Seasonal perspective of dietary arsenic consumption and urine arsenic in an endemic population

Exposure to arsenic in arsenic endemic areas is most remarkable environmental health challenges. Although effects of arsenic contamination are well established, reports are unavailable on probable seasonal variation due to changes of food habit depending on winter and summer seasons, especially for endemic regions of Nadia district, West Bengal. Complete 24-h diets, drinking–cooking water, first morning voided urine samples, and diet history were analyzed on 25 volunteers in arsenic endemic Chakdah block of Nadia district, once in summer followed by once in winter from the same participants. Results depicted no seasonal variation of body weight and body mass index. Arsenic concentration of source drinking and cooking water decreased (p?=?0.04) from 26 μg L^?1 in summer to 6 μg L^?1 in winter season. We recorded a seasonal decrease of water intake in male (3.8 and 2.5 L day ^?1) and female (2.6 and 1.2 L day^?1) participants from summer to winter. Arsenic intake through drinking water decreased (p?=?0.04) in winter (29 μg day^?1) than in summer (100 μg day^?1), and urinary arsenic concentration decreased (p?=?0.018) in winter (41 μg L^?1) than in summer (69 μg L^?1). Dietary arsenic intake remained unchanged (p?=?0.24) over the seasons. Hence, we can infer that human health risk assessment from arsenic needs an insight over temporal scale.     

Characterization and pollution potential assessment of Tunceli, Turkey municipal solid waste open dumping site leachates

Environmental monitoring of leachate quality from an open municipal solid waste dumping site in Tunceli, Turkey was studied in this research. The most commonly examined pollution parameters were determined on a seasonal basis. The annual average 5-day biological oxygen demand (BOD₅) and chemical oxygen demand (COD) values of station points were measured as 70 and 425 mg/L, respectively, and also the average BOD₅/COD ratio (a measure of biodegradability) was calculated as 0.20. The low ratio of biodegradability and slightly alkaline pH values in the leachate samples indicated that the site was characterized by methanogenic conditions. The mean ammonium-nitrogen (NH₄ ⁺-N) and corresponding phosphate (orthophosphate) values were assayed as 70 and 11 mg/L, respectively. The average solids content in the leachates was measured as 4,681 mg/L (total solids) and 144 mg/L (suspended solids). Very low concentrations of iron, manganese, copper, and zinc in the leachate samples were found and the concentration of cadmium was measured below detection limits. Excessive amount of nutrients and high organic and inorganic pollutant content in the leachates pose serious pollution potential to the environment. Since no drainage system or bio treatment exists in this open dumping site, high permeability of natural soil at the site and in the surrounding area and very fractured and crackled rocks under natural soil are indicators of high groundwater pollution potential in this site.     

Arsenic contamination in groundwater and its possible sources in Hanam, Vietnam

This study investigated the arsenic (As) level in groundwater, and the characteristics of aquifer sediment as related to the occurrence of As in groundwater in Hanam, Vietnam. The deposition and transport of As-containing substances through rivers were also examined. Arsenic concentrations in 88% of the groundwater samples exceeded the As limit for drinking water based on the WHO standards. The dominating form of arsenic was As(III). The maximum total As content in bore core sediment was found in a peat horizon of the profiles and generally, elevated levels of As were also found in other organic matter-rich horizons. Total As contents of the bore core sediments were significantly correlated with crystalline iron oxide, silt and clay contents, suggesting that As in aquifer sediment was mainly associated with iron (hydr)oxides and clay mineral. In the groundwater, As concentration showed significant correlations with the total concentrations of Fe and HCO (3)(-). Significant correlations between HCl-extractable As and non-crystalline Fe oxide, total C, N, and S were also observed in the profiles. The results support the hypothesis that under favorable reductive conditions established by the degradation of organic matter, the dissolution of iron (hydr)oxides releases adsorbed As into the groundwater. The deposition of As in the sediments from the Red River were significantly higher than that in the Chau Giang River, suggesting that the Red River is the main source of As-containing substances deposited in the study area.     

Investigation of sequential and enzymatic extraction of arsenic from drinking water distribution solids using ICP-MS

A sequential extraction approach was utilized to estimate the distribution of arsenite [As(iii)] and arsenate [As(v)] on iron oxide/hydroxide solids obtained from drinking water distribution systems. The arsenic (As) associated with these solids can be segregated into three operationally defined categories (exchangeable, amorphous and crystalline) according to the sequential extraction literature. The exchangeable As, for the six drinking water solids evaluated, was estimated using 10 mM MgCl(2) and 10 mM NaH(2)PO(4) and represented between 5-34% of the total As available from the solid. The amorphously bound As was estimated using 10 mM (NH(4))(2)C(2)O(4) and represented between 57-124% of the As available from the respective solid. Finally, the crystalline bound As was estimated using titanium citrate and this represented less than 1.5% of the As associated with the solids. A synthetic stomach/intestine extraction approach was also applied to the distribution solids. The stomach fluid was found to extract between 0.5-33.3 microg g(-1) As and 120-2,360 microg g(-1) iron (Fe). The As concentrations in the intestine fluid were between 0.02-0.04 microg g(-1) while the Fe concentration ranged from 0.06-0.7 microg g(-1) for the first six drinking water distribution solids. The elevated Fe levels associated with the stomach fluid were found to produce Fe based precipitates when the intestinal treatment was applied. Preliminary observations indicate that most of the aqueous Fe in the stomach fluid is ferric ion and the observed precipitate produced in the intestine fluid is consistent with the decreased solubility of ferric ion at the pH associated with the intestine.     

Monitoring the species of arsenic, chromium and nickel in milled coal, bottom ash and fly ash from a pulverized coal-fired power plant in western Canada

The concentration of As, Cr and Ni and their speciation (As3+;5+, Cr3+;6+ and Ni0;2+) in milled coal, bottom ash and ash collected by electrostatic precipitator (ESP) from a coal fired-power plant in western Canada were determined using HGAAS, ICP-AES and XANES. The chemical fractionation of these elements was also determined by a sequential leaching procedure, using deionized water, NH4OAC and HCI as extracting agents. The leachate was analyzed by ICP-AES. Arsenic in the milled coal is mostly associated with organic matter, and 67% of this arsenic is removed by ammonium acetate. This element is totally removed from milled coal after extraction with HCI. Arsenic occurs in both the As3+ and the As5+ oxidation states in the milled coal, while virtually all (>90%) of the arsenic in bottom ash and fly ash appears to be in the less toxic arsenate (As5+) form. Both Ni and Cr in the milled coal are extracted by HCI, indicating that water can mobilize Ni and Cr in an acidic environment. The chromium is leached by water from fly ash as a result of the high pH of the water, which is induced during the leaching. Ammonium acetate removes Ni from bottom ash through an ion exchange process. Chromium in milled coal is present entirely as Cr3+, which is an essential human trace nutrient. The Cr speciation in bottom ash is a more accentuated version of the milled coal and consists mostly of the Cr3+ species. Chromium in fly ash is mostly Cr3+, with significant contamination by stainless-steel from the installation itself.     

Natural attenuation of coal combustion waste in river sediments

The weathering of coal combustion products (CCPs) in a lotic environment was assessed following the Tennessee Valley Authority (Kingston, TN) fly ash release of 2008 into surrounding rivers. Sampled materials included stockpiled ash and sediment collected from 180 to 880 days following the release. Total recoverable concentrations of heavy metals and metalloids in sediment were measured, and percent ash was estimated visually or quantified by particle counts. Arsenic and selenium in sediment were positively correlated with percent ash. For samples collected 180 days after the release, total concentrations of trace elements downstream of the release were greater than reference levels but less than concentrations measured in stockpiled ash. Total concentrations of trace elements remained elevated in ash-laden sediment after almost 2.5 years. A sequential extraction procedure (SEP) was used to speciate selected fractions of arsenic, copper, lead, nickel, and selenium in decreasing order of bioavailability. Concentrations of trace elements in sequentially extracted fractions were one to two orders of magnitude lower than total recoverable trace elements. The bulk of sequentially extractable trace elements was associated with iron-manganese oxides, the least bioavailable fraction of those measured. By 780 days, trace element concentrations in the SEP fractions approached reference concentrations in the more bioavailable water soluble, ion exchangeable, and carbonate-bound fractions. For each trace element, the percentage composition of the bioavailable fractions relative to the total concentration was calculated. These SEP indices were summed and shown to significantly decrease over time. These results document the natural attenuation of leachable trace elements in CCPs in river sediment as a result of the loss of bioavailable trace elements over time.     

Iron-rich Oklahoma clays as a natural source of chromium in monitoring wells

Water samples, drawn from groundwater monitoring wells located southeast of Oklahoma City, OK, were found to contain elevated concentrations of total chromium with an apparent source localized to the area surrounding each well. Since these monitoring wells are located in areas with no historic chromium usage, industrial sources of chromium were ruled out. Water testing was performed on twelve monitoring wells in the area that historically had elevated total chromium concentrations ranging from 10-4900 micrograms per litre. Filtered water samples were found to be free of chromium contamination, indicating that the source of the chromium is the suspended solids. Analysis of these solids by acid digestion and a sequential extraction technique revealed that the chromium was primarily associated with iron-containing solids. X-ray diffraction identified goethite, an iron oxide hydroxide, as the dominant iron-containing phase in the suspended solids. The mineralogy in this region is dominated by interbedded red-bed sandstone and mudstone whose mineral content includes mixed-layer illite-smectite, hematite, goethite, gypsum and dolomite. Elemental analysis of soil samples collected as a function of depth in the locale of the monitoring wells indicated that the iron rich clays contain a natural source of chromium. The elevated levels of total chromium are most likely due to the dissolution of silica and alumina from the chromium containing iron clays in the basic well water, resulting in the release of fine suspended solids that naturally have high chromium concentrations. These results should be applicable to other areas containing iron-rich clays.     

Arsenic and trace metals in river water and sediments from the southeast portion of the Iron Quadrangle, Brazil

The Iron Quadrangle has been one of the most important gold production regions in Brazil since the end of the seventeenth century. There, arsenic occurs in close association with sulfide-rich auriferous rocks. The most abundant sulfide minerals are pyrite and arsenopyrite, yet trace metal sulfides occur in subordinate phases as well. Historical mining activities have been responsible for the release of As and trace metals to both aquatic and terrestrial environments close to mining sites in the region. Therefore, this study was aimed to evaluate the distribution and mobility of As, Cd, Co, Cr, Cu, Ni, Pb, and Zn in streams in the southeast portion of the Iron Quadrangle between the municipalities of Ouro Preto and Mariana, the oldest Brazilian Au mining province. Total concentrations of some trace metals and arsenic in water were determined. The four-stage sequential extraction procedure proposed by the commission of the European Communities Bureau of Reference (BCR) was used to investigate the distribution of these elements in stream sediments. Arsenic concentration in water was >10 ??g L^???1 (maximum limit permitted by Brazilian environmental regulations for water destined for human consumption) at all sampling sites, varying between 36.7 and 68.3 ??g L^???1. Sequential extraction in sediments showed high concentrations of As and trace metals associated with easily mobilized fractions.     

Monitoring of arsenic in aquatic plants, water, and sediment of wastewater treatment ponds at the Mae Moh Lignite power plant, Thailand

Mae Moh is a risky area for arsenic contamination caused by the effluent from biowetland ponds in Mae Moh lignite-fuelled power plant. The objective of this study was to investigate the arsenic concentrations of Mae Moh biowetland ponds and determine the main factors which are important for arsenic phytoremediation in the treatment system. The result revealed that arsenic concentrations in the supernant were in the range of less than 1.0 μg As L^???1 to 2.0 μg As L^???1 while those in the sediment were in the range of 25–200 μg As kg soil^???1. Both values were below the Thailand national standard of 0.25 mg As L^???1 for water and 27 mg As kg soil^???1 for the soil. Arsenic accumulation in the biomass of 5 aquatic plants at the biowetland ponds ranged from 123.83 to 280.53 mg As kgPlant^???1. Regarding the result of regression analysis (R ²?= 0.474 to 0.954), high concentrations of organic matter and other soluble ions as well as high pH value in the sediment could significantly enhance the removal of soluble arsenic in the wetland ponds. From the regression equation of accumulated arsenic concentration in each aquatic plant, Eichhornia crassipes (Mart.) Solms. (R ²?= 0.954), Ipomoea aquatica Forsk. (R ²?= 0.850), and Typha angustifolia (L.) (R ²?= 0.841) were found to be preferable arsenic removers for wastewater treatment pond in the condition of low Eh value and high content of solid phase EC and phosphorus. On the other hand, Canna glauca (L.) (R ²?= 0.749) appeared to be favorable arsenic accumulator for the treatment pond in the condition of high Eh value and high concentration of soluble EC.     

Arsenic content in ground and canal waters of Punjab, North-West India

Groundwater is the primary source of drinking water for more than 95% of the population in Punjab. The world health organization and US Environment Protection Agency recently established a new maximum contaminant level of 10 ppb for arsenic in drinking water. The arsenic concentration of deep water tube wells located in Amritsar city used for domestic supply for urban population ranged from 3.8 to 19.1 ppb with mean value of 9.8 ppb. Arsenic content in hand pump water varied from 9 to 85 ppb with a mean value of 29.5 ppb. According to the safe limit of As, 54% and 97%, water samples collected from deep water tube wells and hand pumps, respectively, were not fit for human consumption. Arsenic content in canal water varied from 0.3 to 8.8 ppb with a mean value of 2.89 ppb. Canal water has got higher oxidation potential followed by deep tube well and hand pump water. The present study suggests the regular monitoring of arsenic content in deep tube well and shallow hand pump waters by water testing laboratories. The consumption of water having elevated concentration of As above the safe limit must be discouraged. In south-western districts of Punjab, it recommends the use of canal water for drinking purposes and domestic use by rural and urban populations than ground water sources.     

Seasonal and spatial variation of arsenic in groundwater in a rhyolithic volcanic area of Lesvos Island,Greece

A survey conducted in water wells located in the rhyolithic volcanic area of Mandamados, Lesvos Island, Greece, indicated that significant seasonal variation of arsenic concentration in groundwater exists mainly in wells near the coastal zone. However, there were differences among those coastal wells with regard to the processes and factors responsible for the observed seasonal variability of the element, although they are all located in a small homogeneous area. These processes and factors include (a) a higher rate of silicate weathering and ion exchange during the dry period followed by the dilution by the recharge water during the wet period, (b) enhanced desorption promoted by higher pH in summer and subsequent dilution of As by rainwater infiltration during the wet period, and (c) reductive dissolution of Mn during the wet period and by desorption under high pH values during the dry period. On the other hand, in wells located in higher-relief regions, the concentration of As in groundwater followed a fairly constant pattern throughout the year, which is probably related to the faster flow of groundwater in this part of the area due to a higher hydraulic gradient. In general, seasonal variation of As in groundwater in the study area was found to be related to geology, recharge rate, topography—distance from coast, and well depth.     

Fractionation of sedimentary arsenic from Port Kembla Harbour, NSW, Australia

The binding of arsenic in sediments of the heavily industrialised Port Kembla Harbour, NSW, Australia, has been investigated. Both dredge and core samples have been used to develop a sieving/sequential extraction (SE) procedure. Dredge samples included oxic surficial and deeper anoxic sediment. The main core sample analysed was 18 cm deep, sliced at 2 cm intervals. Sediment was sieved to three size ranges (<63 microm, 63-250 microm, >250 microm) and each of these was then subjected to a four step SE, sequentially solubilizing arsenic as ion exchangeable, 1 M HCl soluble, NH(2)OH.HCl soluble, and strong oxidising acid soluble. Concentrations of 50-500 mg As kg(-1) were found, elevated well above local background values. The core sample showed elevated concentrations of arsenic within the top 6-8 cm (300-500 mg As kg(-1)), relative to the deeper sediment (100-200 mg As kg(-1)). Substantial portions of the total arsenic present in the 0-8 cm sediments of core and dredge samples, were found to be soluble in 1 M pH 5 phosphate buffer or 1 M HCl. Arsenic in the lower 8-18 cm of the core displayed different solubility, the fourth stage SE strong acid digestion being required to solubilize >90% of the deep sediment arsenic. It appears that diagenesis had resulted in remobilisation of weakly bound arsenic with subsequent diffusion and deposition in surficial layers. Strong acid soluble arsenic present in deeper sediments has two possible origins: sedimented as strongly bound remaining untouched by diagenetic events, or subjected to diagenetic reactions such as pyritization, which lead to more stable crystalline forms of minerals.