Green sporopollenin supported cyanocalixarene based magnetic adsorbent for pesticides removal from water: Kinetic and equilibrium studies.

In this study, magnetic sporopollenin supported cyanocalixarene (MSP-CyCalix) nanocomposite was synthesized and introduced as an adsorbent material for the removal of pesticides from aqueous media. MSP-CyCalix was characterized by different analytical techniques FTIR, SEM, EDX, BET, VSMand TEM. Chlorpyrifos and hexaconazole pesticides were chosen as model analytes solutions for testing the adsorption efficiency of MSP-CyCalix adsorbent. The adsorption results showed that the incorporated cyano functional groups significantly increased the chemical reactivity and adsorption capacity for pesticides. To obtain the highest possible performance, experimental parameters such as pH, salt, dosage and time were optimized. Adsorption kinetics and isotherms models showed that pesticide adsorption process was well fitted with the pseudo-second-order and Langmuir models with a maximum adsorption capacity of 13.88 mg g-1 and 12.34 mg g-1 and a removal efficiency of >90% for both pesticides. Lastly, MSP-CyCalix maintained a removal efficiency of >80% for ten cycles and 60% after the eleventh cycles of usage. The results proved that MSP-CyCalix nanocomposite can be used as an efficient adsorbent for the removal of pesticide residues from water.

Correlation of cadmium and aluminum in blood samples of kidney disorder patients with drinking water and tobacco smoking: related health risk.

The combined exposure to aluminum (Al) and cadmium (Cd) causes more pronounced adverse health effects on humans. The kidneys are the main organs affected by internal exposure to Cd and Al via food and non-food items. The objective of present study was to measure the Al and Cd concentrations in cigarettes tobacco (branded and non-branded) and drinking water (domestic treated, ground and lake water) samples in southern part of Pakistan, to assess the risk due to ingestion of water and inhalation of cigarettes smoke containing high concentrations of both elements. The study population (kidney disorder and healthy) divided into two group based on consuming lake and ground water, while smoking non-branded cigarette as exposed, while drinking domestic treated water and smoking branded cigarette as non-exposed. Electrothermal atomic absorption spectrometry was used to determined Cd and Al concentrations in tobacco, drinking water and blood samples. The resulted data indicated that the levels of Al and Cd in lake and underground water were higher than the permissible limit in drinking water recommended by the World Health Organization. The biochemical parameters of exposed and referent patients, especially urinary N-acetyl-h-glucosaminidase, were used as a biomarkers of kidney disorder. Exposed kidney disorder patients have higher levels of Cd and Al than the exposed referents subjects, while difference was significant when compared to resulted data of non-exposed patients and referents (p = 0.01-0.001). The pearson correlation showed positive correlation between both toxic element concentrations in water, cigarettes versus blood samples of exposed subjects (r = 0.20-0.67 and 0.71-0.82), while lower values were observed for non-exposed subjects (r = 0.123-0.423 and 0.331-0.425), respectively.

Scalp hair and blood cadmium levels in association with chewing gutkha, mainpuri, and snuff, among patients with oral cancer in Pakistan.

BACKGROUND: It has been reported that smokeless tobacco (SLT) chewing can lead to caners of oral cavity. In this study, the relationship between cadmium exposure via consumption of different SLT products by patients with oral cancer with related to referents belongs to different cities of Pakistan are investigated. METHODS: The cadmium in different types of SLT products (gutkha, mainpuri and snuff) consumed by studied population and biological samples (scalp hair and blood) of cancerous and healthy subjects were analyzed. Both referents and patients with cancer have same age group (ranged 30-60 years), socioeconomic status, localities, and dietary habits. The concentrations of cadmium in SLT products and biological samples were measured by electrothermal atomic absorption spectrophotometer after microwave-assisted acid digestion. The validity and accuracy of the methodology were checked by certified reference materials. RESULTS: It was estimated that 10 g intake of different types of gutkha, mainpuri, and snuff could contribute, 18-40%, 15.7-33.6%, and 14-68% of the provisional maximum tolerable daily intake of cadmium, respectively for adults (60 kg). The results of present study showed that the mean value of cadmium was significantly higher in scalp hair and blood samples of patients with oral cancer as compared to those results obtained for referents (P < 0.001). CONCLUSIONS: The high exposure of cadmium due to consuming different SLT products may have synergistic effects with other risk factors associated for oral cancer.

Estimation of calcium, magnesium, cadmium, and lead in biological samples from paralyzed quality control and production steel mill workers.

The determination of trace and toxic metals in the biological samples of human beings is an important clinical screening procedure. The aim of the present study was to compare the level of essential trace and toxic elements cadmium (Cd), calcium (Ca), lead (Pb), and magnesium (Mg) in biological samples (whole blood, urine, and scalp hair) of male paralyzed production (PPW) and quality control workers (PQW) of a steel mill, age ranged (35-55 years). For comparison purposes, healthy age-matched exposed referent subjects (EC), working in steel mill and control subjects (NEC), who were not working in industries and lived far away from the industrial areas, were selected as control subjects. The concentrations of electrolytes and toxic elements in biological samples were measured by atomic absorption spectrometry after microwave-assisted acid digestion. The validity and accuracy of the methodology were checked using certified reference materials. The results of this study showed that the mean values of Cd and Pb were significantly higher in scalp hair, blood, and urine samples of PPW and PQW as compared to NEC and EC (p < 0.001), whereas the concentrations of Ca and Mg were found to be lower in the scalp hair and blood but higher in the urine samples of PPW and PQW. The results show the need for immediate improvements in workplace, ventilation, and industrial hygiene practices.

Comparative evaluation of essential and toxic elements in the blood of kidney failure patients and healthy referents.

The aim of the present study was to evaluate the comparative distribution, correlation, and apportionment of selected elements-aluminum (Al), calcium (Ca), cadmium (Cd), potassium (K), magnesium (Mg), sodium (Na), and lead (Pb)-in the blood samples of male kidney failure patients (KFP) and healthy subjects of age ranged 30-60 years. The blood samples were digested with nitric acid and perchloric acid mixture (2:1), followed by the quantification of elements by atomic absorption spectrometry. The concentration of essential elements in blood samples of KFP were found in the range of Ca (97-125), Mg (18-36), Na (2971-3685), and K (177-270) mg/L while, the levels of Al, Cd, and Pb were found in the range of (475-1275), (0.9-9.9), and (211-623) µg/L, respectively. In the healthy referents, concentration of electrolytes in blood samples was lower than KFP, but difference was not significant (p > 0.05). While the levels of toxic elements in blood samples of referents were three- to sixfold lower than KFP (p < 0.01). Principal component analysis (PCA) and cluster analysis (CA) of the element data manifested diverse apportionment of the selected elements in the blood sample of the KFP compared with the healthy counterparts.

Preconcentration and determination of lead and cadmium levels in blood samples of adolescent workers consuming smokeless tobacco products in Pakistan.

The present study was aimed to evaluate the cadmium (Cd) and lead (Pb) levels in the blood samples of adolescent boys, chewing different smokeless tobacco (SLT) products in Pakistan. For comparative purpose, boys of the same age group (12-15 years), not consumed any SLT products were selected as referents. To determine trace levels of Cd and Pb in blood samples, a preconcentration method, vortex-assisted liquid-liquid microextraction (VLLME) has been developed, prior to analysis by flame atomic absorption spectrometry. The hydrophobic chelates of Cd and Pb with ammonium pyrrolidinedithiocarbamate were extracted into the fine droplets of ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate, while nonionic surfactant, Triton X-114 was used as a dispersing medium. The main factors affecting the recoveries of Cd and Pb, such as concentration of APDC, centrifugation time, volume of IL and TX-114, were investigated in detail. It was also observed that adolescent boys who consumed different SLT products have 2- to 3-fold higher levels of Cd and Pb in their blood samples as compared to referent boys (p < 0.001).

Assessment of selenium and mercury in biological samples of normal and night blindness children of age groups (3-7) and (8-12) years.

The causes of night blindness in children are multifactorial and particular consideration has been given to childhood nutritional deficiency, which is the most common problem found in underdeveloped countries. Such deficiency can result in physiological and pathological processes that in turn influence biological sample composition. This study was designed to compare the levels of selenium (Se) and mercury (Hg) in scalp hair, blood, and urine of night blindness children age ranged (3-7) and (8-12) years of both genders, comparing them to sex- and age-matched controls. A microwave-assisted wet acid digestion procedure was developed as a sample pretreatment for the determination of Se and Hg in biological samples of night blindness children. The proposed method was validated by using conventional wet digestion and certified reference samples of hair, blood, and urine. The Se and Hg in biological samples were measured by electrothermal atomic absorption spectrometry and cold vapor atomic absorption spectrometry, prior to microwave acid digestion, respectively. The concentration of Se was decreased in scalp hair and blood samples of male and female night blindness children while Hg was higher in all biological samples as compared to referent subjects. The Se concentration was inversely associated with the risk of night blindness in both genders. These results add to an increasing body of evidence that Se is a protecting element for night blindness. These data present guidance to clinicians and other professional investigating deficiency of essential micronutrients in biological samples (scalp hair and blood) of night blindness children.

Distribution of arsenic, cadmium, lead, and nickel levels in biological samples of Pakistani hypertensive patients and control subjects.

BACKGROUND: The abnormal metabolism of metal ions plays an important role in health and disease conditions, and studies about them have been attracting significant interest. The aim of our study was to assess the toxic elements arsenic (As), cadmium (Cd), nickel (Ni), and lead (Pb) in biological samples (scalp hair, blood, urine) of 387 hypertensive males and females, aged between 30 and 60 years, from an urban population together with 439 non-hypertensive subjects, of the same age group and residential areas. METHODS: The element concentrations were measured by means of an electrothermal atomic absorption spectrophotometer after microwave-induced acid digestion. The validity and accuracy was checked by conventional wet acid digestion method and using certified reference materials. The overall recoveries of all elements were found in the range of 96.8 - 99.4% of certified values. RESULTS: The results indicated significantly higher levels of As, Cd, Ni, and Pb in the biological samples (scalp hair, blood and urine) of hypertensive patients, when related to controls of both genders. CONCLUSIONS: The high exposure of toxic elements may be synergistic with risk factors associated with hypertension. These data present guidance to clinicians and other professionals who will be investigating the toxicity of heavy elements in biological samples (scalp hair and blood) of hypertensive patients.

Evaluation of chromium and manganese in biological samples (scalp hair, blood and urine) of tuberculosis and diarrhea male human immunodeficiency virus patients.

BACKGROUND: The consequence of trace elements deficiency has been associated with an increased risk of human immunodeficiency virus type 1 (HIV-1) disease progression and mortality. This study examined the association between high concentrations of chromium (Cr) and manganese (Mn) in scalp hair, blood, and urine and opportunistic infections in hospitalized patients with the acquired immune deficiency syndrome (AIDS). METHODS: The study was performed on 62 male HIV+ patients (HIV-1) from different cities of Pakistan. The patients were divided in two groups according to secondary infections (tuberculosis, diarrhea, or high fever). The biological samples (scalp hair, blood and urine) were collected from AIDS patients, and for comparative study 120 healthy subjects (males) of same age group (31 - 45 years), socio-economic status, localities, and dietary habits were also included. The elements in the biological samples were analyzed by electrothermal atomic absorption spectrophotometry after microwave-assisted acid digestion. The validity and accuracy of the methodology was checked by using certified reference materials (CRMs) and with the values obtained by conventional wet acid digestion method on the same CRMs. RESULTS: The results indicated significantly lower concentrations of Cr and Mn in the biological samples (scalp hair, blood, and urine) of male HIV-1 patients, compared with control subjects. It was observed that the lower levels of these trace elements may be predictors for secondary infections in HIV-1 patients. There was a significant decrease in mean values of Cr and Mn in whole blood and scalp hair, whilst higher concentrations were observed in urine samples of the three groups of AIDS patients as compared to a controlled healthy male group (p < 0.001). CONCLUSIONS: Low Cr and Mn levels may be due to increased Cr and Mn losses. These data present guidance to clinicians and other professional investigating deficiencies of Cr and Mn in biological samples of AIDS patients.

Arsenic content in smokeless tobacco products consumed by the population of Pakistan: related health risk.

Extensive investigation has shown that smokeless tobacco (SLT) may cause inflammation of the oral cavity. In this study, the concentration of arsenic (As) was determined in SLT products (gutkha, mainpuri, and dry and moist snuff). Scalp hair samples of males aged 20-30 years who consumed different types of SLT products available in Pakistan were analyzed for As contents. Total As in different SLT products and in scalp hair was determined by electrothermal atomic absorption spectrometry after microwave-assisted extraction. The validity of the methodology was tested by simultaneously analyzing certified reference materials and spike recovery studies. The range of As concentrations in moist snuff, dry snuff, gutkha, and mainpuri were 0.574-1.53, 0.642-1.07, 0.246-0.622, and 0.419-0.874 µg/g, respectively. We estimated that a daily intake of 10 g of all SLT products could contribute 2.0-12.2% of the provisional maximum tolerable daily intake for As in adults. The As concentration in scalp hair of SLT consumers was higher than that of referents who had not consumed any type of tobacco products.

Evaluation of fresh and stored rainwater quality in fluoride and arsenic endemic area of Thar Desert, Pakistan.

In the current study, the chemistry of fresh and stored rainwater of Thar Desert, Pakistan, was estimated during two consecutive monsoon periods. The present research deals with the variation in physicochemical parameters, total arsenic (As(t)), inorganic arsenic species (As(i), As(V), As(III)), and fluoride (F(-)) in stored rainwater (SRW) at different time intervals (1 week to 3 months). The pH of fresh rainwater (FRW) samples showed slightly acidic to neutral in nature (6.08-7.06) which were inconsistent with the reference pH value (5.6) of rainwater. The resulted data indicated that As(t) and F(-) levels in SRW were enhanced with time duration. The levels of As(t) and F(-) in SRW after different time intervals were found in the range of 194-683 µg/L and 10-35.4 mg/L, respectively. The values of As(t) and F(-) were 20-70 and 7-24 times higher than those of WHO permissible limits, 10 µg/L and 1.5 mg/L, respectively. The As(III) was dominant species in SRW, which corresponds to >60 % of As(i). The characteristics of the SRW revealed an unacceptable quality to consume for drinking and agricultural purposes in the studied area.

Evaluation of status of arsenic, cadmium, lead and zinc levels in biological samples of normal and arthritis patients of age groups (46 - 60) and (61 - 75) years.

BACKGROUND: Arthritis is a chronic inflammatory disease resulting in inflammation of diarthrodial joints (particularly joints of hands, wrists, feet, knees, ankles, and shoulders), manifested by swelling and functional impairment. This study was designed to evaluate the levels of the toxic elements arsenic (As), cadmium (Cd), and lead (Pb) and correlate those with the essential trace element zinc (Zn) in biological samples (scalp hair, blood, and urine) of arthritis patients, in two age groups (46 - 60 and 61 - 75) of both genders. For comparison purposes all three biological samples were collected from gender- and age-matched non-arthritic subjects as referents. METHODS: The As, Cd, and Pb in biological samples were analysed by electrothermal atomic absorption spectrometry, prior to microwave assisted acid digestion. The level of Zn was determined by flame atomic absorption spectrometry. The validity and accuracy of the methodology was checked by using Certified Reference Materials (CRM) from the Community Bureau of Reference (BCR) of the Commission of the European Community and with those values obtained by conventional wet acid digestion method on the same CRMs. RESULTS: The results of this study showed that the mean values of As, Cd, and Pb were higher in blood, scalp hair, and urine samples of arthritis patients as compared to those values obtained in age-matched referent subjects. The concentration of Zn was lower in the biological samples of rheumatoid arthritis patients of both genders with respect to non-arthritic subjects. The urinary levels of the elements studied were found to be higher in the arthritis patients than in the age-matched healthy referents (p < 0.001). CONCLUSIONS: An inverse correlation was observed between Zn and toxic elements in biological samples of arthritis patients (r = 0.612 - 0.754). Intake of certain antioxidant micronutrients, particularly a zinc supplement, may protect against the development of rheumatoid arthritis.

Evaluation of calcium, magnesium, potassium and sodium in biological samples of male human immunodeficiency virus patients with tuberculosis and diarrhea compared to healthy control subjects in Pakistan.

BACKGROUND: Electrolyte deficiency has been associated with an increased risk of human immunodeficiency virus type 1 (HIV-1) disease progression and mortality. This study examined the association between low electrolyte concentrations in blood and scalp hair and the presence of opportunistic infections in patients with acquired immune deficiency syndrome (AIDS). METHODS: Sixty-two male HIV positive patients (HIV-1) from various cities in Pakistan were recruited to the study. These Patients were divided into two groups according to secondary infections (tuberculosis and high fever with diarrhea), and biological samples (scalp hair, serum, blood and urine) were collected from them. As a comparative control group, 120 healthy subjects (males) of the same age group (31 - 45 years), socio-economic status, localities and dietary habits were also included in the study. The elements in the biological samples were analyzed by flame atomic absorption spectrophotometry after microwave-assisted acid digestion. Validity and accuracy of the methodology were checked using certified reference materials (CRMs) and against values obtained by a conventional wet acid digestion method on the same CRMs. RESULTS: The results indicated significantly lower levels of calcium, potassium, magnesium and natrium in all analyzed biological samples (blood, serum and scalp hair) of male patients with Acquired Immune Deficiency Syndrome (AIDS) in comparison to healthy controls (p < 0.01), while the levels of these elements were found to be higher in urine samples of the AIDS patients than in those of the control group. CONCLUSIONS: These data offer guidance to clinicians and other professionals investigating the deficiency of electrolytes in biological samples (scalp hair, serum and blood) of AIDS patients in relation to healthy subjects.

Evaluation of chromium, cobalt and manganese in biological samples (scalp hair, blood, and urine) of Pakistani viral hepatitis (A-E) patients and controls.

BACKGROUND: The aim of the present study was to compare the level of chromium (Cr), cobalt (Co), and manganese (Mn) in biological samples (blood, urine, and scalp hair) of patients suffering from different types of viral hepatitis (A, B, C, D, and E; n = 521) of both genders, ages ranging from 31 - 45 years. For comparative study, 255 age-matched control subjects of both genders residing in the same city were selected as referents. METHODS: The digests of all biological samples were analysed for Cr, Co, and Mn by electrothermal atomic absorption spectrometry (ETAAS). The validity and accuracy of the methodology was checked by using certified reference materials (CRMs) and compared with those values obtained by conventional wet acid digestion method on same CRMs. RESULTS: The results of this study showed that the mean values of Cr, Co, and Mn were higher in blood and scalp hair samples of hepatitis patients than in age-matched control subjects. The urinary levels of these elements were found to be higher in the hepatitis patients than in the age-matched healthy controls (p <0.001). CONCLUSIONS: These results are consistent with literature-reported data, confirming that the overload of these trace elements can directly cause lipid peroxidation and eventually hepatic damage.

Distribution of copper, iron, and zinc in biological samples of Pakistani hypertensive patients and referent subjects of different age groups.

BACKGROUND: The abnormal metabolism of metal ions plays an important role in health and disease conditions, and studies about them have been attracting significant interest. The aim of our study was to assess the trace metals (copper (Cu), iron (Fe), and zinc (Zn)) in biological samples (scalp hair, blood, urine) of 387 hypertensive males and females, age range 30 - 60 years, from an urban population and 439 non-hypertensive subjects of same age group and residential areas. METHODS: The element concentrations were measured by means of an atomic absorption spectrophotometer after microwave-induced acid digestion. The validity and accuracy was checked by conventional wet acid digestion method, using certified reference materials. The overall recoveries of all elements were found in the range of 95.2 - 98.7 % of certified values. RESULTS: The results indicated significantly lower levels of Cu, Fe, and Zn in the biological samples (blood and scalp hair) of hypertensive patients when compared to referents of both genders while the levels of these elements was found to be high in urine samples of hypertensive patients as compared to referents. CONCLUSIONS: The deficiency of Cu, Fe, and Zn may be synergistic with risk factors associated with hypertension. These data present guidance to clinicians and other professionals who will be investigating the deficiency of essential micronutrients in biological samples (scalp hair, serum, and blood) of hypertensive patients.

Simultaneous preconcentration of toxic elements in artificial saliva extract of smokeless tobacco product, mainpuri by cloud point extraction method.

It has been extensively investigated that smokeless tobacco chewing can lead mainly to inflammation of oral cavity. In present study, the total and artificial saliva extracted toxic elements, arsenic, cadmium, nickel and lead were estimated in smokeless tobacco product, mainpuri. Cloud point extraction has been used for the preconcentration of arsenic, cadmium, nickel and lead in artificial saliva extract, using complexing reagent, ammonium pyrrolidinedithiocarbamate. Total and extractable toxic elements were measured by electrothermal atomic absorption spectrometry. The chemical variables of cloud point extraction were optimized. The validity of methodology was tested by simultaneously analyzing certified reference material (Virginia tobacco leaves) and spike recovery test. The artificial saliva extractable levels of arsenic, cadmium, nickel and lead ranged from 15-22, 45-70, 35-58, and 18-32%, respectively, of total elemental contents in mainpuri samples. It was estimated that intake of 10g of different brands of mainpuri contributing the 5.88, 55.0, 45.0 and 40.3% of the provisional maximum tolerable daily intake for arsenic, cadmium, nickel and lead, respectively for adults of ~60kg.

Analysis of cadmium, nickel, and lead in commercial moist and dry snuff used in Pakistan.

The extent to which smokeless tobacco endangers human health is an ongoing subject of debate. In this study, concentrations of toxic metals, cadmium (Cd), lead (Pb), and nickel (Ni), were measured in different snuff products (dry brown and black and moist green and brown), available and consumed in Pakistan. Concentrations of Cd, Pb, and Ni were determined in 23 samples of various brands of snuff by electrothermal atomic absorption spectrometry, after microwave-assisted acid digestion. The reliability of methodology was assured by analyzing certified reference material. The resulted data of toxic metals in different snuff products are comparable to the existing information with limited exceptions. It was estimated that 10 g intake of different types of snuff could contribute 14-68, 17-47, and 20-73 % of the provisional maximum tolerable daily intake for Cd, Ni, and Pb, respectively.

Chromium Exposure in the Adult Population, Consuming Different Types of Smokeless Tobacco Products in Pakistan.

The pervasive smokeless tobacco (SLT) consumption and diseases related to its use is a hot topic for the public discussion. In this study, concentrations of chromium (Cr) were measured in different SLT products [snuff (dry and moist), mainpuri, and gutkha] offered and used in Pakistan. The current study was also designed to assess the Cr levels in the biological (scalp hair and blood) samples of male and female subjects, age ranged from 25 to 60 years, chewing different SLT products. For comparative purpose, the healthy persons of the same age group, who did not consume any SLT products, were selected as referents. The concentrations of Cr in SLT products and biological samples were measured by electrothermal atomic absorption spectrophotometer after microwave-assisted acid digestion. The validity and accuracy of the methodology were checked by certified reference materials (CRMs). The resulted data indicated that the adult persons, who consumed different SLT products, have 2-3 fold higher levels of Cr in biological samples as compared to referent subjects (p < 0.01). The persons, who chew/sniff different SLT products, have 50-80 and 42-82 % higher levels of Cr in their scalp hair and blood samples as related to referents. The daily intake of Cr is lower as compared to the recommended value of 50-200 µg/day. It was expected that 10 g consumption of various kinds of SLT products (snuff, mainpuri, and gutkha) may subsidize 21.2-220, 17.7-122, and 18.4-273 % of the recommended daily intake of Cr, respectively.

Simultaneously removal of inorganic arsenic species from stored rainwater in arsenic endemic area by leaves of Tecomella undulata: a multivariate study.

In the present study, an indigenous biosorbent (leaves of Tecomella undulata) was used for the simultaneous removal of inorganic arsenic species (As(III) and As(V)) from the stored rainwater in Tharparkar, Pakistan. The Plackett-Burman experimental design was used as a multivariate strategy for the evaluation of the effects of six factors/variables on the biosorption of inorganic arsenic species, simultaneously. Central composite design (CCD) was used to found the optimum values of significant factors for the removal of As(III) and As(V). Initial concentrations of both inorganic As species, pH, biosorbent dose, and contact time were selected as independent factors in CCD, while the adsorption capacity (q e) was considered as a response function. The separation of inorganic As species in water samples before and after biosorption was carried out by cloud point and solid-phase extraction methods. Theoretical values of pH, concentration of analytes, biosorbent dose, and contact time were calculated by quadratic equation for 100 % biosorption of both inorganic As species in aqueous media. Experimental data were modeled by Langmuir and Freundlich isotherms. Thermodynamic and kinetic study indicated that the biosorption of As(III) and As(V) was followed by pseudo second order. It was concluded that the indigenous biosorbent material efficiently and simultaneously removed both As species in the range of 70.8 to 98.5 % of total contents in studied ground water samples. Graphical abstract Optimizing the significant varable by central 2(3) + star orthogonal composite design.