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Pollutant analysis by spectroscopy methods

5 TH Course of Chemistry Degree

Jos Antonio Alonso Domnguez

Roco Barreiro Rodrguez

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Introduction

Toxicity of the inorganic arsenic

Legislation

Analytical methods

Literature sources

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Arsenic is a chemical element whose namecomes from the Greek 'Aarsenkon', meaning'powerful'.

It was obtained around 1250 by AlbertoMagno heating arsenic oxide with soap.

Are known compounds of arsenic from

antiquity, were used as a poison because ofits extreme toxicity. In contrast, from arsenicalso got the first effective medicine to treatsyphilis.

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Historically there have beenmajor disasters due to arseniccontamination. An example of adisaster that remains today is in

Bangladesh .

The University of California,Berkeley after working forseveral weeks camp closed its

report warning "a tragedy thatexceeds 10 times that ofChernobyl

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In Argentina, more than a 100locations in the provinces ofBuenos Aires, La Pampa, Salta,

San Luis, Cordoba and other is arate of As contained in drinkingwater.

The origin of the problem is thevolcanic ash resulting from theformation of the Andes, whichcontaminate groundwater.

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The environmental contamination and mobilityof arsenic is conditioned primarily by the

redox conditions and the pH of the waterenvironment. The phosphate, if it is present ina concentration greater than arsenic, will actas a competitor In the arsenic fixation.

Arsenic comes in various

oxidation states, As0, or as ions:

As5 +, As3 +, and As3-.

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Regarding the diabetogenic effect ofarsenic, (Tseng et al. 2004), proposesoxidative stress and interference withfactor of transcription as the most likelycauses. Through induction of insulinresistance and beta cell dysfunction.

Arsenite at low concentration, inhibitsan important nuclear receptor ofhormones, that activate the insulin.

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The epidemiological studies in Taiwan, Chile, Argentina and

Mexico showed that arsenic was diabetogenic.

In Taiwan, in studies carried out inrecent decades confirms theassociation between exposure toarsenic and disorders such asdiabetes mellitus, hypertension,heart disease, stroke.

More recent studies suggest thatthe risk of disease is associatedwith the inability of the individual tofully methylate inorganic arsenic.

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In Mexico, a study recognized by the AMC shows that exposure toArsenic is a clear risk factor for disease development.

In rats was found that low-dose arsenic, pancreatic beta cells did notdie, however, it was observed that the cells lost their ability torecognize the extracellular glucose concentration.

It was also concluded that arsenic interferes insulin secretion byaltering levels of intracellular free calcium.

80 individuals were studied, which were 50% are diabetics. Inconclusion, when it came to diabetic patients, it was found that the

higher the concentration of arsenic in the urine, the percentage ofbeta cell function declines with an exponential pattern, although itwas noted that arsenic exposure seems to be sufficient to trigger thedisease but it is a clear risk factor that should be taken into account.

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Millions of individuals worldwide are exposed to drinking

water contaminated with inorganic arsenic (arsenite and

arsenate) mainly from natural mineral deposits.

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Inorganic arsenic is classified by the U.S. EPA as a knownhuman carcinogen, based on extensive population studies

of lung cancers following inhalation exposure, and skin

cancers following ingestion of contaminated drinking water

in adults.

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Other effects of chronic arsenic exposure reported foradults include kidney damage and failure, anemia, low

blood pressure and shock, and central nervous system

symptoms such as headaches, weakness, and delirium.

Chronic arsenic exposure of children and adults has been

associated with adverse liver and respiratory effects,

including irritation of mucous membranes.

During development, chronic high level inorganic arsenic

exposure in humans was associated with increased

incidence of preterm delivery, miscarriage, stillbirths, low

birth weight, and infant mortality.

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Inorganic arsenic exposure during childhood wasassociated with decreased performance in tests of

intelligence (I.Q.) and long-term memory.

Acute exposure (14 days or less, including single exposure)of adults and children resulted in gastrointestinal effects,

such as nausea, vomiting, abdominal pain, and diarrhea;

and neurological effects (e.g., headaches, dizziness) on the

central and peripheral nervous system.

Acute one-time exposure of adults of approximately 22-600

g/day has resulted in death.

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Furthermore, inorganic arsenic may be an increased risk ofdiabetes in chronically-exposed adults and children

because relatively high concentrations increased glucose

and insulin levels, decreased glucose uptake in insulin

sensitive cells and interfered with transcription factorsinvolved in insulin signal transduction and insulin sensitivity

in vitro.

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Additionally, humans are exposed to organic arseniccompounds such as arsenobetaine and arsenosugars,

mainly from seafood, but they are nontoxic.

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In Spain until 1990 the level of arsenic allowed in drinkingwater was 100g/L.

It was not until October 3, 1990 when the Royal Decree1138/90 was approbed. This RD which sets the limit for

drinking water in 50g/L, this limit is still too high if weconsider the limit recommended by the World HealthOrganization which is set at 10g/L.

From Europe, Directive 98/83/EC sets the limit of 10g/L limitcoinciding with the WHO recommendation and EPA but not

until January 7, 2003 when enters into force transposing thestandard European to Spain by approval the RealDecreto140/2003 establishing health criteria of drinking waterin countries with severe arsenic poisoning.

Argentina would not adopt this limit of 10g/L to 2007.

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In Spain have not been established ceilings of inorganicarsenic in aliments.

Currently, Australia and New Zealand only limited to 1mg/kgfresh weight of inorganic arsenic content in fish products.

World Health Organization has set the limit for wet weight foodof 2 mg/Kg. The limits for shellfish is 50 to 100 mg/Kg and forfish 3 to 5 mg/kg.

In actually is presenting a bill to limit the amount of arsenic

allowed in rice and rice-based products, following aninvestigation by Consumer Reports found that very high levelsof arsenic in more than 200 samples of this cereal and itsderivatives.

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There are many analytical methods for the determination

of inorganic arsenic. The most used are:

HG-ICP-MS

HG-AAS Electroanalysis

Others:

IC-ICP-MS AFS

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HPLC-HG-ICP-MS

A cyclonic spray chamber was connected to the T piece and the sample gas flow mixed with thenebulised continuous internal standard creating stable wet plasma conditions. For the analysis,the ICP-MS was optimised for optimal sensitivity and stability on arsenic that has an m/z of 75.

The sample flow was passed through a reaction coil of Teflon into a gas-liquid separator. Thegaseous products were transported via an argon flow to a glass T piece connected directly to the

torch.

An HPLC system was connected directly to a continuous-flow HG system. Acid (3 M, HCl) andNaBH4 (1.5% w/v, in 0.1M NaOH) were mixed with the sample post column via two T pieces.

Acid and NaBH4 flows were regulating using a peristaltic pump.

The separation and detection of anionic arsenic species in the sample extracts were carried outon a column with a flow rate of 1 mLmin-1. As mobile phase, 6.2 mM NH4NO3 and 6.5 mM

H3PO4 adjusted to a pH of 6.0 was used.

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HPLC-HG-ICP-MS

Schematic of HPLC-HG-ICP-MS system:

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SPE-HG-AAS

The hydrides were swept to a gasliquid separator using argon gas and transported through a

dryer tube to the electrically heated open-ended T-shaped silica cell of the atomic absorptionspectrometer. Data were collected by the SOLAAR software.

The HG-AAS system was operated according to the manufacturers instructions. Theautosampler introduced the pre-reduced sample to the vapour generator where it reacted withfreshly prepared NaOH/NaBH4 (0.5%w/v) and HCl (4.7 M) solutions to generate gaseousarsenic

hydrides (AsH3) from AsIII.

A pre-reduction was carried out by mixing 1 mL of SPE eluate with 7 mL of reduction solution,which react for 1 h at room temperature. Furthermore, 6 ml of 3 M HCl was added, and it was left

to react for another hour at room temperature.

Inorganic arsenic was selectively separated from other arsenic compounds using strong anionexchange SPE. Optimal performance was obtained using a silica-based SPE cartridge with a

flow rate of ~1 mlmin1. The procedure required a pre conditioning and a post analysis wash ofthe cartridge .

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SPE-HG-AAS

HG-AAS system:

SPE cartridge:

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ELECTROANALYSIS: Differential-puIseCathodic Stripping Voltammetry

Auxiliary electrode: platinum rod

Reference electrode: Ag/AgCl/KCl(3 M) Working electrode: an HMDE

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ELECTROANALYSIS:

The initial potential was set at -0.5 V and, after extrusion of a new mercury drop, arsenic wascollected with stirring for 120 s. The stirrer was stopped and, after a 20 s rest period, the scan was

begun in the negative direction using the differential-pulse (DP) mode with an electrode area of0.50 mm2, a sweep rate of 6.6 mVs-l and a pulse modulation of -50 mV.

A 0.2 g amount of KI and 0.4 g of NaHC03 were weighed in the voltammetric cell and then 10 mlof concentrated HCl and 10 ml of water were added. After dissolution, a volume of soil solution

(50-200 L) was added to the cell.

After the samples had reached room temperature, they were filtered and diluted to 50 mL withwater. These solutions were passed through a Sep-Pak C18 cartridge, previously activated with 5

mL of methanol and 10 mL of water.

Soil samples were dried, homogenized and sieved. A 0.5 g amount of soil was weighed in a PTFEbeaker, 2 ml of concentrated HNO3 and 6 ml of concentrated HCl were added and the beaker wasclosed and placed in the microwave digester. Digestion was carried out with the sample treatedfor 10 min at a pressure of 120 psi with a maximum power of 650 50W.

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Ana Navas-Acien, Ellen K. Silbergeld, Roberto Pastor-Barriuso, Eliseo Guallar, ArsenicExposure and Prevalence of Type 2 Diabetes in US Adults, J. Am. Med. Assoc., 300/7(2008) 814-822.

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E.M., Feldmann, J., HPLC-HG-ICP-MS: a sensitive and selective method for inorganicarsenic in seafood, Anal. Bioanal. Chem. (2012) 404:21852191.

Rasmussen, R.R., Hedegaard, R.V., Larsen, E.H., Sloth, J.J., Development and validationof an SPE HG-AAS method for determination of inorganic arsenic in samples of marine

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