Use of Some Natural Materials to Reduce Concentrations of some Heavy Metals in Polluted Water and Possibility of Using Them for Irrigation in Calcareous Agricultural Soils

To evaluate efficiency of some natural materials in using them as filters to reduce concentrations of some heavy elements in polluted water, and possibility of using them for irrigation in calcareous agricultural soils, two experiments were conducted, first is laboratory, which is treatment of various polluted waters, namely industrial water, gray water, and river water using three natural treatment materials as filters, which are activated charcoal, Eichhornia crassipes plant powder, Ceratophyllum plant powder. Poles made of polyethylene were used with a length of 100 cm and a diameter of 10 cm equipped with a tap from bottom, a layer of glass wool was placed at bottom, and then treatment materials were placed on top of it at a height of 50 cm. A piece of gauze cloth was placed over it for filter polluted water from solids. Polluted water was passed after filtering from top of column and left for 24 hours for equilibrium, then filtrate was collected from bottom of column. Second experiment, it is biology, as an experiment was conducted in pots of 20 kg capacity, using calcareous soil with a Loamy texture, and Dodonaea seedlings (one of fence plants) were planted. NPK fertilizers were added to it according to fertilizer recommendation, and irrigation was done with tap water after 50% of available water was depleted by gravimetric method. Results showed the following: 1-High concentrations of heavy metals, each of Lead, Ccadmium, Zinc and Nickel in industrial water, where they reached 5.190, 0.043, 3.727 and 0.371 mg L-1, respectively, exceeding limits allowed by World Food and Health Organization for each of Cadmium, Zinc and Nickel, while concentrations of Lead is within internationally permitted limits. As for gray water, Cadmium concentrations exceeded internationally permitted limits, while concentrations of Lead, Zinc and Nickel were within internationally permitted limits. In river water, they were within internationally permitted limits. 2. Decreased concentrations of heavy metals in polluted water treated with various natural treatment materials compared to their concentrations before treatment. The materials used in treatment can be arranged according to their efficiency in adsorption of heavy metals from industrial and gray water as follows: -activated charcoal > Eichhornia crassipes powder > Ceratophyllum powder > Arundo donax plant_powder. 3-High available concentrations of heavy metals in soils passed through polluted water compared to soils irrigated with treated water. Total concentrations were 34.436, 18.227, 8.064 mg kg-1 soil, 31.064, 16.884, 6.190 mg kg-1 soil, 32.860, 12.670, 4.930 mg kg-1 soil, 0.465, 3.680, and 0.590 mg kg-1 soil for Lead and Cadmium elements and Zinc and Nickel in succession and industrial water and gray water and river water successively, after 100 days of cultivation. 4-High concentrations of heavy metals in plants irrigated with different polluted water compared to plants irrigated with different treated water after 100 days of cultivation. Plants irrigated with polluted and treated water can be arranged according to concentration of heavy metals in them as follows: - industrial water > gray water > river water.


Introduction
Problem of water scarcity is one of most important problems facing people in various living and economic fields, such as industry, agriculture and tourism, which pushes people to use low-quality water, such as industrial wastewater and gray water.Use of some chemical compounds to get rid of heavy metals is an approach that is harmful to environment.Use of natural materials instead of chemicals to remove heavy metals from polluted water is an environmentally friendly approach.Heavy metal pollution is a serious problem facing humans and other organisms due to their lack of biodegradation and their accumulation in living organisms [1].As environment has become increasingly and rapidly polluted by these elements due to industrial progress and widespread urbanization, which poses a threat to ecosystem represented by soil, surface and groundwater Finally, food security and human health.There are many sources of heavy elements in ecosystem that come with wastewater streams such as electroplating, smelting, paint pigments, batteries, mining and agricultural activities [2].Two main sources of heavy metals in soil are natural chemistry background of earth and pollution resulting from various human activities.
[3] showed an increase in accumulation of Cadmium in roadsides as a result of vehicle exhaust and agricultural sites due to addition of chemical fertilizers to it.Soil is main basin for elements emitted into environment from a wide range of human sources [4].Accumulation of heavy metals in agricultural soils is a growing concern due to its relationship with food safety, or its access by leaching into groundwater, as well as surface waters represented in nearby rivers and water bodies, which may lead to potential health risks.[5] show that water pollution with heavy metals is one of the most important environmental problems across world.[6] showed different quantitative standards for pollution with Cadmium, Lead and Nickel for soils and plants on sides of road in some areas of Baghdad governorate.[7] showed that irrigation with water contaminated with heavy metals such as Lead increases its total concentration in soil, according to levels of addition.[8] showed that increased pollution with Lead, Cadmium and Nickel in soil and plant tissues growing in soils contaminated with these elements and close to industrial facilities.Term gray water refers to all wastewater generated from domestic use, with exception of sanitation wastewater, which comes from bathrooms , washing dishes, sinks and kitchen sinks.Gray water from kitchens contains food residues and high amounts of oils, fats, and substances.It is the least polluted type of water.They contain shampoo and soap powders such as Sodium, Phosphate and Nitrogen.[9] showed that irrigation with water contaminated with heavy metals leads to accumulation of these elements in soil and makes it polluted [10] showed that activated charcoal has a high surface area and has a high adsorption capacity for heavy metals from industrial wastewater.[11] showed that adsorption of heavy metals on charcoal is by forming complexes with active groups of OH-1 and COO -1 on surface of charcoal.[12] and Aldaini and [13] indicated high ability of charcoal to adsorb heavy metal ions such as Lead, Nickel, Cadmium and other contaminated waters due to large number of small pores in its composition.Adsorption mechanism of heavy metals on activated charcoal includes electrostatic interference, ion exchange, chemical precipitation, and complexation with active aggregates on surfaces of charcoal granules [14 and 15].[16] and [17] showed that activated charcoal has ability and high efficiency of adsorption of Copper ions from its solutions.[18] found, when evaluating quality of industrial water coming out of Cotton textile factory in Al-Kadhimiya, that it was contaminated with Zinc and Lead, which are among most common elements in textile waste, whose concentrations were 0.098 and 0.030 mg L -1 , respectively.[19] showed presence of a high percentage of heavy metals such as Lead, Cadmium, Iron and Manganese in irrigation water due to discharge of water from factories and hospitals.[20] studied evaluation of soil contamination and some vegetable plants with heavy metals irrigated from water table generated from Baiji refinery, and showed that industrial waste water led to a decrease in percentage of germination and natural growth of plants and led to an increase in concentration of Cadmium in irrigated water, as its concentration rate was 0.025 mg L -1 Thus, it exceeded limit allowed by World Health Organization for irrigation water, and in soil, Nickel concentrations increased significantly.It amounted to 006 mg kg -1 , excelled on critical limits set by World Health Organization.As for plant models, concentration of Lead was high in most models above permissible limit, as it reached 1.80, 0.37, 1.80, 1.00 mg kg -1 dry material for each of celery and Pepper, Tomato and Alfalfa in succession.A study by [21] showed possibility of using Nile flower powder in the treatment of industrial wastewater, which proved to be highly efficient and less expensive than the use of various physical and chemical methods, and that the process of adsorption of Eichhornia crassipes leaves is a new technique for cleaning environment, such as treating polluted water on one hand and getting rid of Eichhornia crassipes flower plant, on the other hand.[22] showed possibility of using Ceratophyllum leaves in biological treatment to remove Lead, Cadmium and Copper combined, results showed a Lead removal rate of 80%, Ceratophyllums excelled in Cadmium removal rate to more than 90%.Research aims to know role of some natural and organic materials in purification of polluted water and the possibility of using them for agricultural purposes in calcareous soils.

Materials and Methods
Two experiments were conducted, first is laboratory to treat polluted water (industrial wastewater and gray water) , second is biological in pots to use treated polluted water for irrigation.In the treatment experiment, natural and organic materials were used (as filters), which are activated charcoal, Eichhornia crassipes plant powder, Ceratophyllum plant powder.These materials were dried, ground and sifted with a sieve with a diameter of 4 mm .itused solid polyethylene columns with a length of 100 cm and a diameter of 10 cm.Column is open from top and closed from bottom, and is equipped with a tap, in order to control process of opening and closing column.A layer of glass wool was placed at bottom of column to avoid clogging tap first ,A part of treatment material was avoided coming down to bottom secondly, then treatment material was placed on top of it (each separately) at a height of 50 cm, columns were rammed well to maintain approximately equal weights.The polluted water was passed after filtration with a piece of safari cloth to rid it of solid materials (hair or wool and other coarse solid materials), from top of column to fullness of column leaving a height of 3 cm from top and remained for 24 hours for balancing process.Treatment materials were replaced every two days, after that filtrate was collected in tanks of polyethylene for using it in irrigation in biological experiment, and a sample of filtrate was taken in each treatment process and kept in polyethylene containers for conducting required chemical analyzes after two drops of Tolouien were added to it to prevent microbial growth.Second experiment, it is biological, where a potting experiment was conducted in plastic house using calcareous soil with a loamy texture .Soil was air-dried, ground and passed through a sieve with a diameter of 4 mm for the purpose of planting in plastic pots with a capacity of 20 kg with diameters of 33 cm, a base diameter of 23 cm and a height of 23 cm.A layer of glass wool was placed at bottom for disleaking soil out of pots, pots were filled with soil.then it was tamped several times to obtain an apparent density similar to soil of field.A part of soil was taken and dried air-conditioned, then ground and sifted with a sieve with a diameter of 2 mm for conducting some chemical and physical analyses before planting (Table 1)Dodonaea seedlings (one of the vegetable hedge plants) were planted in pots.NPK fertilizers were added according to soil fertilizer recommendation.Watering was done with tap water after depleting 50% of water available to plant by gravimetric method.Different types of water were used for irrigation.Experiment included three factors: water quality (polluted water, including industrial wastewater and gray water).River water was also used as a treatment compared to one experimental unit with three replicates, treatment materials (active charcoal, Eichhornia crassipes plant powder, Ceratophyllum plant powder) and water quality (treated and polluted)Thus, number of experimental traetments : 2(water quality) x 3 (treatment materials) x 2 (water quality) x 3 (replicates) = 36 Some physical and chemical properties of soil, water and plants were estimated according to methods presented in.[23] and [24].Total heavy metalss in soil (Pb 2+ , Zn 2+ , Ni 2+ , Cd 2+ ) were estimated after digesting soil using concentrated sulfuric acid and perchloric acid, by atomic absorption apparatus (AAS) and according to method presented in [23].Available heavy metals (Pb 2+ , Zn 2+ , Ni 2+ , Cd 2+ ) were extracted from soil using chelated compound (DTPA) (Diethylene triamine penta aceticacid) according to method of [25] and estimated using atomic absorption apparatus (AAS).Total content of heavy metals in plant (Cd, Pb, Ni and Zn) was estimated after digestion of samples (shoot and root) by means of a mixture of two acids (HCLO4 -H2SO4) and was measured by atomic absorption apparatus [26].Water class was determined according to the US Salinity Laboratory (USDA) systems.

Concentration of some Heavy Metals in Materials used in Biological Treatment
Lead concentration for each of Eichhornia crassipes plant powder, Ceratophyllum plant powder was 66.78, 56.86 mg kg -1 dry matter, respectively, while Cadmium concentration was 1.86, 1.37, 1.05 mg kg -1 dry matter, for each of Eichhornia crassipes plant powder, Ceratophyllum plant powder, and Charcoal, respectively ( Table 2), concentration of Lead and Cadmium in all materials used in bioremediation, with the exception of Charcoal, excelled on limits allowed globally in plants according to World Food and Health Organization [27] of Lead 5.00 mg kg -1 dry matter, Cadmium 0.20 mg kg -1 dry matter.Zinc.Its concentrations reached 53.49, 41.12, Nickel 32.76, 24.21 mg kg -1 dry matter, for each of Eichhornia crassipes plant powder, Ceratophyllum, respectively.[27] of 60 mg kg -1 dry matter, for Zinc and 67 mg kg -1 dry matter, for Nickel,As for Charcoal, there was no record of Zinc and Nickel because it is porous carbonaceous materials burned.High concentrations of heavy metals in materials used in bioremediation are due to fact that most aquatic plants have a high ability to absorb heavy metals from water.This is in line with what [28] mentioned, who showed that most aquatic plants have ability to absorb heavy metals in water and sediment by roots and their ability to accumulate these elements in aquatic plants and be used as a vital indicator of accumulation of heavy metals in water.Eichhornia crassipes plant powder excelled on Ceratophyllum is due to vegetation and its large root, and this is consistent with what [29] mentioned, which showed that Nile flower has ability to absorb some heavy metals from surrounding aquatic environment.

Heavy Metals in Polluted Water (Untreated)
Table 3 shows high concentration of heavy metals, each of Lead, Cadmium, Zinc and Nickel in industrial water, where they amounted to 5.190, 0.043, 3.727 and 0.371 mg L -1, respectively, and it excelled on critical limits allowed by World Food and Health Organization [27], in gray water, concentrations of Lead, Zinc, and Nickel were within internationally permitted limits, amounting to 4.491, 1.314, and 0.166 mg L -1 , respectively, except for concentration of Cadmium, which exceeded internationally permitted limits of 0.01 mg L -1 , where concentration reached 0.036 mg L -1 , while all concentrations of river water were within internationally permitted limits, where they amounted to 0.257, 0.01, 0.913, and 0.03 mg L -1 for above elements, respectively.Increase in concentration of Lead, Cadmium, Zinc and Nickel in polluted water, including industrial water, is due to fact that most of this water is produced from wastes of industrial facilities, which contain heavy metals in different concentrations.This is consistent with what [30] mentioned, who showed that most factories deliberately dispose of their waste and products of their industries, such as factory waste, oil derivatives, city waste, chemical fertilizers, pesticides, disease-causing organisms, and radioactive materials by dumping them into water such as oceans, seas, and rivers, so that they become water is less suitable for natural uses such as drinking and agriculture.[31], who showed that most important sources of Cadmium pollution are industry and mining.As for gray water, high concentration of Cadmium in it is due to products and waste of laundry and cleaning water, such as soap, shampoo, and brighteners, which contain cadmium at a higher concentration than rest of studied elements.
Table 3. Concentrations of heavy metals (mg L -1 ) in polluted water used in agriculture.

Treated Industrial Water
Concentrations of Lead, Cadmium, Zinc and Nickel in industrial water treated by activated charcoal were 0.340, 0.002, 0.157, and 0.029 mg L -1, respectively, and those treated with Eichhornia crassipes plant powder were 1.210, 0.008, 1.120, and 0.066 mg L -1 , respectively.andtreatment with Ceratophyllum plant 1.430, 0.016, 1.260 and 0.074 mg L -1 , for ions of above elements in succession (Table 4),Natural materials played an important role in reducing concentrations of heavy metalts in polluted industrial water and increasing removal rate, where it reached 93.44% when using Charcoal, 94.52% for Lead and Cadmium, 95.79% for Zinc and 92.19% for Nickel.Activated charcoal had a preference for Zinc ion adsorption, excelled on Cadmium ion and Lead, and least adsorption of Nickel.This is consistent with what [32] mentioned, who showed that percentage of Lead, Nickel and Cadmium removal using charcoal was 95.52%, 92.13% and 65.13%, respectively.The concentration of these heavy metals was within internationally permitted limits [27] for irrigation water, which is less than 5.00, 0.01, 2.00, and 0.20 mg L -1 for Lead, Cadmium, Zinc and Nickel, respectively.Eichhornia crassipes plant powder played an important role in reducing concentrations of heavy metals from polluted industrial water, where removal percentage was 76.69% for Lead, 81.74% for Cadmium, 70.00% for Zinc, and 82.21% for Nickel.Eichhornia crassipes plant powder had a preference in adsorption of Nickel ion, superior to Cadmium ion and Lead, and least adsorption of Zinc ion, concentration of ions of these heavy metals was within internationally permitted limits [27] for irrigation water.Ceratophyllum powder played a major role in reducing the concentrations of heavy metals from polluted industrial water, as removal percentage was 74.19% for Lead, 63.47% for Cadmium, 66.20% for Zinc and 80.06% for Nickel.Ceratophyllum powder had a preference in adsorption of Nickel ion, superior to Lead and Zinc ions, lowest was Cadmium ion, concentration of ions of these heavy metals was within internationally permitted limits [27] for irrigation water except for Cadmium, which exceeded internationally permitted limits for irrigation water, which is less than 0.01 mg L -1 Activated charcoal was highly efficient in industrial water treatment, excelled on Eichhornia crassipes plant powder, then Ceratophyllum powder.The order of organic materials in terms of efficiency in the adsorption of heavy elements from industrial water was as follows: charcoal > Eichhornia crassipes > Ceratophyllum powder.

Treated Gray Water
Concentrations of Lead, Cadmium, Zinc and Nickel in water treated by charcoal were 0.296, 0.009, 0.002 and 0.003 mg L -1 , respectively, while treatment by Eichhornia crassipes plant powder reached 1.060, 0.016, 0.110 and 0.053 mg L -1 , respectively.Ceratophyllum powder, they were 1.180, 0.014, 0.122, and 0.087 mg L -1 , respectively, respectively (Table 4).Natural materials played an important role in reducing concentrations of heavy metals from polluted gray water, where removal rate using activated charcoal was 93.00% for Lead, 75.00% for Cadmium, 99.85% for Zinc, and 98.20% for Nickel.Activated charcoal had a preference in adsorption of Zinc ions, excelled on Nickel ions, then Lead, least adsorption was to Cadmium ion, concentration of ions of these heavy metals was within internationally permitted limits [27] for irrigation water, which are less than 5.00, 0.01, and 2.00 and 0.20 mg L -1 each for Lead, Cadmium, Zinc and Nickel, respectively.Eichhornia crassipes plant powder played an important role in reducing concentrations of heavy metals from polluted gray water, where removal percentage for Lead reached 76.40%, Cadmium 69.44%, Zinc 91.63%, and Nickel 68.07%.Preference of Eichhornia crassipes plant powder in adsorption of Zinc ions was excelled on Cadmium and Lead ions lowest adsorption was Nickel ions, concentrations of these heavy metals were within internationally permitted limits [27] for each of Lead, Zinc and Nickel, respectively, with exception of Cadmium, which excelled on limits the internationally permitted amount of irrigation water is less than 0.01 mg L -1 .Ceratophyllum powder had a major role in reducing concentrations of heavy metals from polluted gray water, removal percentage for Lead was 73.72%, 61.11% for Cadmium, 90.72% for Zinc, and 47.60% for Nickel.Ceratophyllum powder had a preference in adsorption of Zinc ions, excelled on Lead and Cadmium ions, least adsorption of Nickel ions, concentration of ions of these heavy metals was within internationally permitted limits [27] for each of Lead, Zinc and Nickel, respectively, with exception of Cadmium, which excelled on internationally permitted limits Activated charcoal had high efficiency in treating polluted sewage water, superior to Eichhornia crassipes plant powder, then Ceratophyllum powder, and less than Arundo donax plant powder.Reason for high efficiency of activated charcoal in removing heavy metals from various polluted waters is attributed to large number of pores on its internal and external surfaces, these sites are active in adsorption process.Presence of active groups that represent active sites in adsorption phenomenon such as carboxylate, carboxylic anhydride, phenolic, carbonyl and lactone, Eichhornia crassipes plant powder, it worked to reduce concentrations of heavy metals with high efficiency, and this shows its ability to absorb these elements, this is consistent with [21] who showed possibility of using Eichhornia crassipes plant powder in treatment of industrial wastewater, which proved high efficiency and less cost than use of physical methods different chemicals, process of adsorption of Eichhornia crassipes plant powder for pollutants is a new technique for cleaning environment, such as treating polluted water on one hand, and getting rid of Eichhornia crassipes plant powder on other hand.Ceratophyllum, they had their role in purifying polluted water from Lead and other elements and improving quality of treated water.This is in line with what [33] mentioned, who noticed efficiency of Ceratophyllum plant in reducing values of pollution indicators and improving water quality when compared with values of those indicators in water leaving heavy water filtration station.

Concentration of Available Heavy Metals in Soil Irrigated with Different Polluted Waters
Concentrations of heavy metals in soil irrigated with artificial water after 100 days of cultivation were 8.934, 0.203, 6.125 and 0.915 mg kg -1 soil for Lead, Cadmium, Zinc and Nickel, respectively (Table 5).Soils irrigated with gray water, available concentrations of Lead, Cadmium, Zinc and Nickel were 4.250, 0.131, 1.530 and 0.488 mg kg -1 soil, respectively, while soils irrigated with river water were 0.370, 0.031, 1.873 and 0.143 mg kg-1 soil, respectively, for heavy metals, respectively.Table 5. Concentration of available heavy metals in soil irrigated with different contaminated waters after 100 days of cultivation (mg kg -1 soil).Concentrations of the available elements of Lead, Cadmium, Zinc and Nickel were 0.370, 0.031, 1.873 and 0.143 mg kg -1 soil, respectively, for the heavy metals, respectively.Increased available of these elements soil after irrigating soil with polluted water may be due to increase in accumulated total concentrations as a result of irrigation with polluted water and increase in root growth and root secretions that lower the pH of soil and increase readiness of these elements.Concentration of available Lead was superior in soil irrigated with gray water, reaching 7.741 mg kg -1 soil, successively.It was excelled on soils irrigated with industrial water, whilelowest was in soils irrigated with river water, as it amounted to 0.170 mg kg -1 soil successively.This may be due to low soil interaction values for gray water compared to other water types (Table 3), In addition to activity of plants roots and their secretions are higher, which increased available Lead in soil irrigated with gray water, this is consistent with what [34] mentioned, which indicated that Lead is present in soil forming organic complexes or in form of water oxides close to surface, movement of Lead in soil depends on degree of soil reaction (pH) and its content of organic matter.Available Cadmium, it excelled in soils irrigated with gray water on rest of soils irrigated with different waters, as it reached 0.174 mg kg -1 soil, because concentration of Cadmium was high in industrial water, which caused deterioration of plant condition and lack of Cadmium absorption with decomposition of plant parts after its death.This is consistent with [35] who showed that Cadmium causes a decrease in rate of photosynthesis in plant and a decrease in rate of absorption of water and nutrients, so symptoms of yellowing and blackening of roots appear on them, and thus their death.Lowest concentrations were in soil irrigated with river water, as it reached 0.031 mg kg -1 soil.Available Zinc and Nickel, it excelled in soil irrigated with industrial water compared to other types of water, concentrations reached 6.125 mg kg -1 soil for Zinc and 0.699 mg kg -1 soil for Nickel.kg -1 soil in succession.Increase of Zinc and Nickel in industrial water is due to its increased concentrations in it, in addition to secretion of humic acids by roots of plants, which work to lower pH of soil with passage of time, total concentration of these elements decreases and available concentration increases, as well as plant absorbs it with decomposition of plant parts after its death.Decrease in the available concentration of Lead, Cadmium, Zinc and Nickel in soil irrigated with river water, it is attributed to low concentrations of these elements in river water, in addition to good growth of plant, which increased plant's activities and increased absorption of these elements.This is consistent with what [36] mentioned, who showed that plants used in bioremediation have a high ability to absorb heavy metals from soil or extract them through plant roots, and they have a high ability to accumulate these elements in their roots, which have a high growth rate.

Concentration of Heavy Metals in Plants Irrigated with Different Polluted Waters
Concentrations of studied elements in plants irrigated with industrially polluted water were 58.48, 0.565, 32.33 and 20.46 mg kg-1 dry matter, for each of Lead, Cadmium, Zinc and Nickel, respectively (Table 6).Concentrations of Lead, Cadmium, Zinc and Nickel in plants grown in soil irrigated with gray water were 51.219, 0.410, 24.106 and 16.830 mg kg -1 dry matter, respectively, concentrations of these elements in plants in soil irrigated with river water reached 9.613, 0.196, 20.206 and 0.350.mg kg -1 dry matter sequentially.Concentrations of heavy metals in plants irrigated with industrial water were superior to plants irrigated with gray water and were lowest in plants irrigated with river water.Gray water may be due to accumulation of these elements in soil as a result of irrigation with this polluted water, plant absorbs them in addition to what is secreted by the root zone of various substances that lower pH of soil and thus increase readiness of heavy elements, and their absorption increases with passage of time by plant more, Concentrations of Pb and Cd in plants irrigated with industrial water and gray water excelled on internationally permitted limits in plant by [27], which amounted to 5.00 mg kg -1 dry matter for Pb, and 0.20 mg kg -1 dry matter for Cd (except for concentration of Cd in soil irrigated by river water).This is consistent with what [37] found, who showed a general increase in concentrations of heavy metals in studied plants close to sources of pollution compared to same plants that are relatively far from sources.Concentration of Zn and Ni in plants irrigated with industrial water, gray water and river water, it did not excelled on internationally permissible limits in plants [27] of 60.00 mg kg -1 and 67.00 mg kg -1 dry matter for Zn and Ni.Table 6.Concentration of heavy metals in plants irrigated with different polluted waters after 100 days of cultivation (mg kg -1 dry matter).

Concentration of Available Heavy Metals in Soil Irrigated with Treated Industrial Water
Available concentration of Pb, Cd, Zn and Ni was 1.319 in soil irrigated with industrial water treated with Charcoal and 0.019, 0.974 and 0.388 mg kg -1 soil for heavy metals, respectively.Concentrations in soil irrigated with industrial water treated by Eichhornia crassipes plant powder, they were 2.413, 0.019, 2.260 and 0.421 mg kg -1 soil for heavy metals, respectively,while concentrations in soil irrigated with industrial water treated by Ceratophyllum were 2.028, 0.200, 2.243 and 0.407 mg kg -1 soil for above heavy metals, respectively (Table 7), treated materials reduced available concentrations of Pb, Cd, Zn and Ni in soil irrigated with treated industrial water compared with soil irrigated with polluted industrial water due to adsorption of these elements by treated materials, each according to its efficiency and ability to adsorption according to active and effective sites that it possesses.Lead, Cadmium, Zinc and available Nickel were superior in soil irrigated with industrial water treated by means of the Eichhornia crassipes plant powder over water treated by Ceratophyllum, and finally in water treated by Charcoal, so treated materials can be arranged in terms of their efficiency in bio treatment as follows: Table 7. Concentration of available heavy metals in soil irrigated with treated water after 100 days of cultivation (mg kg -1 ).Increase in concentrations of available heavy metals in soil may be due to accumulation of these elements in soil as a result of irrigation with this water containing these elements.Then plant absorbs them as a result of secretions in root zone, which in turn lowers soil-pH and thus increases available of studied heavy metals.This is consistent with what.[37] showed, who showed high concentrations of heavy metals in plants close to sources of pollution compared to same plants that are relatively far from them.Sources of pollution.

Concentration of Available Heavy Metals in Soil Irrigated with Treated Gray Water
Table 7 shows available concentration of Pb, Cd, Zn and Ni in soil irrigated with gray water treated with Charcoal, as it reached 1.317, 0.019, 0.509 and 0.211 mg kg -1 soil for heavy metals, respectively.In the case of treatment with Eichhornia crassipes plant powder, it reached 2.414, 0.107, 0.881, and 0.301 mg kg -1 soil, while when using Ceratophyllum it was 2.347, 0.098, 0.784, and 0.280 mg kg -1 soil heavy mrtals, respectively.Treated materials worked to reduce available concentrations of Pb, Cd, Zn and Ni in the soil irrigated with treated gray water because of their adsorption by treated materials, each according to its efficiency and ability to adsorption according to active and effective sites present in it.Soils are as follows: Charcoal > Ceratophyllum > Eichhornia crassipes plant powder  [27], which amounted to 5 mg kg -1 dry matter.Concentration of Cadmium in all plants irrigated with industrial water treated with various materials excelled on internationally permissible limits in th plant (0.20 mg kg -1 dry matter), did not excelled on concentration of Zinc in all plants irrigated with industrial water treated with various materials.Internationally permitted limits in plants set by [27] amounted to 60.00 mg kg -1 dry matter, Nickel concentrations in all plants irrigated with industrial water treated with various materials did not excelled on internationally permitted limits in plants specified by [ 27] amounting to 67.00 mg kg-1 dry matter.It is noted from above results that Charcoal, Ceratophyllum , and finally Eichhornia crassipes plant powder was excelled in their efficiency to reduce concentrations of heavy metals in treated water with various treated materials, It can be arranged according to its efficiency in removing heavy elements as follows: Charcoal > Ceratophyllum > Eichhornia crassipes.Charcoal excelled on rest of processing materials in its high efficiency to reduce concentrations of heavy metals is due to large number of pores present in it due to imbalance in crystalline structure of coal during its production, and this increases its ability to adsorb ions of various elements [38],In addition, it has many effective fluids such as carboxyl groups, phenols, and others that increase adsorption of heavy metals [39].Increase in concentration of heavy metals may be due to ability of plants to absorb heavy metals with age and store them in their roots, stems and leaves, this is consistent with what [40] mentioned, who showed that concentrations of these elements increase in plants as a result of plant growth in contaminated soil.treated gray water excelled on international permissible limits for Pb per plant set by [27] of 5 mg kg -1 dry matter, Concentration of Cd in all plants irrigated with treated gray water excelled on internationally permissible limits per plant set by [27] amounting to 0.20 mg kg -1 dry matter, it did not exceed.Concentration of Zn and Ni in all plants irrigated with gray water treat internationally permitted limits in plant and set by [27] amounting to 60.00 and 67.00 mg kg -1 dry matter for the two components in succession.Different treatment materials can be arranged in removing heavy metals from polluted gray water, which is reflected in concentrations.Heavy elements in plants irrigated with this treated water are as follows: -.Charcoal > Ceratophyllum > Eichhornia crassipes.Higher concentration of heavy metals in plants irrigated with gray water treated by Eichhornia crassipes plant powder and Ceratophyllum powder may be attributed to increase in heavy metals originally present in these two plants before their use in bioreclamation process compared to 1259 (2023) 012011 IOP Publishing doi:10.1088/1755-1315/1259/1/01201111 cane powder, in which concentrations of heavy metals were low before using it.Charcoal has excelled in increasing its efficiency in process of biological reclamation as a result of increasing its internal pores as well as those on surface, as well as containing effective aggregates that increase process of adsorption of heavy metals from polluted water.This is consistent with what [41] mentioned, who indicated presence of active groups such as carboxyl group and phenol in coal, which increase the adsorption process and thus reduce heavy metals from water contaminated with it.

Table 1 .
Some chemical and physical properties of the study soil before cultivation.

Table 2 .
Concentration of some heavy metals in materials used in bio treatment.

Table 4 .
Concentrations of heavy metals (mg.L -1 ) in treated water used in agriculture.
Plants Irrigated with Treated Water 3.8.1.Concentration of Heavy Metals in Plants Irrigated with Treated Industrial Water Concentrations of Lead, Camium, Zinc and Nickel in plants irrigated with industrial water treated with activated charcoal were 18.552, 0.187, 13.185, and 9.928 mg kg -1 dry matter (Table 8),while concentrations in plants irrigated with industrial water treated by Eichhornia crassipes plant powder, they were 26.224, 0.280, 22.241, and 12.206 mg kg -1 dry matter of above heavy metals, successively, in plants irrigated with industrial water treated by Ceratophyllum powder 27.980, 0.250, 21.644, and 11.102 mg.kg -1 dry matter for the above heavy metals in succession,.Lead, Cadmium, Zinc and Nickel in plants irrigated with industrial water treated with Eichhornia crassipes plant powder were excelled on Ceratophyllum powder, lowest concentrations were in water treated by activated charcoal.Concentration of Lead in all plants irrigated with treated industrial water exceeded internationally permissible limits in plant and set by 10

Table 8 .
Concentration of heavy metals in plants irrigated with treated water after 100 days of cultivation (mg kg -1 dry matter).
Table 8 shows concentrations of Pb, Cd, Zn and Ni in plants irrigated with gray water treated with activated charcoal, which amounted to 17.866, 0.138, 6.211 and 3.711 mg kg -1 dry matter, respectively.plants irrigated with gray water treated with Eichhornia crassipes plant powder, they were 23.238, 0.219, 11.398, and 4.771 mg kg -1 dry matter, respectively.and in plants irrigated with gray water treated with Ceratophyllum powder, it amounted to 22.774, 0.201, 11.749, and 13.864 mg kg -1 dry matter for heavy metalss.successively, Pb, Cd, Zn and Ni were superior in plants irrigated with gray water treated with Eichhornia crassipes plant powder on Ceratophyllum powder, lowest concentrations were in gray water treated with activated charcoal.Concentration of Pb in all plants irrigated with