View of Analysis of heavy metals in waters, sediments, and blood clams (Anadara granosa) in the pond at Sidoarjo Regency

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JOURNAL OF MARINE RESOURCES AND COASTAL MANAGEMENT INDONESIAN JOURNAL OF MARINE LIFE AND UTILIZATION

e-ISSN: 2722-0966 Vol. 4 Issue 1

Analysis of heavy metals in waters, sediments, and blood clams (Anadara granosa) in the pond at Sidoarjo Regency

Andika Keessa Saputra*, Asri Sawiji and Dian Sari Maisaroh

Marine Science Department, Faculty of Science and Technology, UIN Sunan Ampel Surabaya, Indonesia

As industry continues to develop, both the oil and gas industry, agriculture and other non-oil and gas industries, the level of environmental pollution in Sidoarjo Regency is also increasing. Heavy metals are one of the pollutants in domestic waste and industrial waste which can affect river water quality and can have negative impacts on humans and the environment. The aim of this research is to determine the concentration of the heavy metals lead (Pb) and cadmium (Cd) in water, sediment and blood clam meat, determine the maximum consumption limit for the heavy metals Pb and Cd contained in blood clams, and determine relationship between Pb and Cd concentrations in waters, sediments and blood clams at research study, Tambak Cemandi and Banjar Kemuning station. The sampling method in this research used random sampling. Testing for heavy metals Pb and Cd uses Atomic Absorption Spectrophotometry (AAS). The research results showed that the concentrations of heavy metals Pb and Cd in the waters, sediments and blood clams at the research location had exceeded the established safe limits. Pearson correlation analysis showed that there was no significant relationship between Pb and Cd concentrations in waters, sediments and blood clams.

Keywords: Anadara granosa, Atomic Absorption Spectrophotometry, cadmium, heavy metals, lead

INTRODUCTION

Sidoarjo Regency as one of the pillars of the capital city of East Java Province is an area that is experiencing rapid development. This development was achieved because the various potentials that exist in the region such as industry and trade, tourism, and small and medium enterprises can be well packaged and targeted.

However, with the development of industries, such as oil and gas, agriculture and other non-oil and gas industries, environmental pollution is increasing [1]. Waters are an area that is rich in biological and non-biological natural resources, where this diversity can have its own impact on regional or national economic growth and development.

However, the allocation of water resources on a large scale can also lead to high levels of pollution in water bodies, resulting in ecosystem damage [2].

Pollutants that are harmful to the environment include waste containing heavy metals. Heavy metal pollution can occur in water bodies and also in the form of solid substances in the water, such as sediment. Heavy metal pollution in aquatic ecosystems is closely related to the release of heavy metals from domestic waste, industry and other human activities [3,4]. Heavy metals can potentially pollute waters, one of which is pond waters in Sedati District, Sidoarjo Regency. Lead (Pb) and cadmium (Cd) are types of heavy metals that can potentially pollute the pond waters of Sedati District, which can come from industrial activities, in the form of the plastics industry which is one of the industries that can produce cadmium (Cd) while for lead (Pb) can come from paper industry

waste, fishing activities, airport activities and domestic waste.

One tool for assessing water quality in an area is biomonitoring. Biota can act as a bioindicator of whether heavy metal pollution has occurred in waters, one of which is shellfish. Bioindicators are biotic elements that act as guides, the presence of these bioindicators can indicate changes in water quality caused by human activities or natural damage [5]. Polluted aquatic ecosystems can affect the survival of the organisms that inhabit them, including shellfish which have limited mobility and settle in aquatic sediments, being vulnerable to the presence of pollutants such as the entry of heavy metals into water bodies [6]. Blood clams (Anadara granosa) are a type of shellfish that are often found in Sedati waters and are used by the local community as a catch.

Heavy metal Pb and Cd poisoning can cause acute and chronic poisoning. Acute lead poisoning is characterized by a burning sensation in the mouth and irritation of the gastrointestinal tract accompanied by diarrhea, while symptoms of chronic poisoning are characterized by nausea, anemia and abdominal pain and can result in paralysis. Meanwhile, the chronic effects of Cd metal poisoning usually result in kidney damage, nervous system damage, and damage to some of the kidney tubules [7]. Therefore, this study aims to determine heavy metal levels, maximum consumption limits, and the relationship between water parameters and the heavy metal concentration lead (Pb) and cadmium (Cd) in water, sediment, and blood clams (Anadara granosa) meat.

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METHODS

The research was conducted in March-November 2022 at two stations, i.e. Tambak Cemandi and Banjar Kemuning, Sedati District, Sidoarjo Regency (Figure-1).

This research uses a descriptive method. Descriptive research aims to make systematic, factual, and accurate explanations, descriptions of the facts, characteristics, and relationships between the phenomena studied [8]. The field sampling technique was carried out using the simple random sampling method. Simple random sampling is a method of selecting a sample from a simple random population so that each member of the population has the same opportunity to be included in the sample. All members of the population become members of the sampling frame. When the population is homogeneous, a simple random sample is usually used [9].

Figure-1. Research Sites

Analysis of levels of Lead (Pb) and Cadmium (Cd) in water, sediment, and blood clam meat was carried out by Method Atomic Absorption Spectrophotometer (AAS) at the Surabaya Industrial Research and Consultation Center. The atomic absorption spectrometry method was chosen because it is very sensitive, simple, inexpensive, easy and fast, and requires a small sample.

AAS analysis is more sensitive, specific for the elements indicated, and can be used to determine very small amounts of elements without prior separation [10].

Determination of the safe limit for consuming blood shells or the body's resistance to heavy metals in foods that can be eaten within a week is carried out by calculating the Maximum Tolerable Intake (MTI). The formula used in determining the MTI [11] shown in Equation (1).

𝑀𝑇𝐼 =^𝑀𝑊𝐼_𝐶𝑡 (1) where MTI is the maximum tolerance limit of consumption level (kg/week), Maximum Weekly Intake (MWI) is the maximum consumption rate limit per week (mg/week) and the value is determined using the formula as shown in Equation (2), and Ct is the metal concentration in fish meat (mg/kg).

𝑀𝑊𝐼 = 𝐵𝑊 × 𝑃𝑇𝑊𝐼

(2) where BW is the average body weight of adults and children (kg) in Indonesia according to the Indonesian Ministry of Health (2010) is 50 kg for adults and 15 kg for children. Provisional Tolerable Weekly Intake (PTWI) is the maximum tolerance value (mg/kg). JECFA (Joint FAO/WHO Expert Committee on Food Additive) 2004 and Indonesian National Standard (SNI) 7387:2009 stipulates the maximum level of heavy metal pollution in food or consumption tolerance figures per week for foodstuffs containing Pb 25 µg/kg and Cd 7 µg/kg.

The relationship between the concentration of Pb and Cd between water and sediment and blood clam at the research location analysed with Pearson correlation analysis. Correlation analysis is a statistical method for determining a quantity that indicates a strong relationship between a variable and other variables. The higher the correlation value, the closer the relationship between the two variables. If the correlation number is close to one, then the correlation between the two variables is getting stronger. Conversely, when the correlation coefficient is close to zero, the correlation between the two variables decreases [12]. If the significance value of the test results is more than 0,05 (sig >0,05), then there is no relationship, and if the significance value is less than 0,05 (sig < 0,05), then there is a relationship between variables [13].

RESULTS AND DISCUSSIONS Concentration of Pb and Cd In Waters

The results of observations of the heavy metal concentration in water at the Tambak Cemandi and Banjar Kemuning stations showed that the average value of the heavy metal Pb was 2.5 ppm and 1.96 ppm respectively, while the average value of the heavy metal concentration Cd was 1.14 and 0.75 ppm (Table-1).

The concentration of the heavy metal Pb in the waters at both stations exceeds the threshold stipulated in the Government Regulation of the Republic of Indonesia Number 82 of 2001 concerning Quality Management and Control of Water Pollution, i.e. 0.03 ppm.

This can be influenced by the environment around the Tambak Cemandi and Banjar Kemuning stations where there are industries in the river flow such as the paper and pulp industry which have the potential to produce liquid waste containing the heavy metal Pb [14].

Apart from being influenced by industry, the high level of heavy metal Pb can also be influenced by domestic waste and fishing activities (coming from peeling paint on pipes and residual combustion materials from motorized boats used as a means of transportation) which can trigger an increase in heavy metal Pb pollution in waters [15,16].

Table-1. Concentration of Pb and Cd in waters

No Station Heavy

metal Average (ppm) 1 Tambak Cemandi

Pb 2,5±0,372

Banjar Kemuning 1,96±0,096

2 Tambak Cemandi

Cd 1,14±0,050

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Saputra, K. A., et. al. / Journal of Marine Resources & Coastal Management 4 (1): 11-17, January 2023 Likewise, the concentration of the heavy metal

Cd in the waters at both stations exceeds the threshold of 0.01 ppm. The plastic industry located around the study location has the potential to influence the high level of heavy metal Cd pollution in the river flow [17]. Spills of diesel fuel and domestic waste also contribute to Cd contamination in the area [18].

The high value of these heavy metals, both Pb and Cd, can be toxic to life in the ecosystem itself and if it contaminates humans, it can enter through the mouth, breath or skin, it is also very toxic to the body so it can cause disability and, more fatally, cause death [19].

Concentration of Pb and Cd In Sediments

The results of observations of the heavy metal concentration Pb and Cd in sediment showed that the average value of the heavy metal Pb at the Tambak Cemandi station was 14.44 mg/Kg, while the average value of the concentration at the Banjar Kemuning station was lower at 11.1 mg/kg. The average value of the heavy metal Cd concentration at the Tambak Cemandi station was 2.9 mg/kg, while the average value at the Banjar Kemuning station was lower, 2.5 mg/kg. The results of the heavy metal concentration Pb and Cd in the sediments of Tambak Cemandi and Banjar Kemuning stations are shown in (Table-2).

Table-2. Concentration of Pb and Cd in sediments

No Station Heavy

Pb 14,44±1,571

2 Tambak Cemandi

Cd 2,9±0,324

The concentration of the heavy metal lead in the sediment has not exceeded the threshold, while the results for the heavy metal concentration cadmium have exceeded the threshold. According to the Swedish Environmental Protection Agency (SEPA) 2000, the quality standard for the heavy metal lead in sediment is 25 mg/Kg and the quality standard for the heavy metal cadmium in sediment is 0.2 mg/kg.

Heavy metals in sediment, such as the heavy metals Pb and Cd in the Tambak Cemandi and Banjar Kemuning ponds, can become pollutants if their concentration exceeds the specified threshold. Heavy metals enter water bodies and are deposited in sediments through three stages: deposition, adsorption, and absorption by aquatic organisms. Heavy metals in the aquatic environment are absorbed into particles and accumulate in sediments. Heavy metals have the property of bonding with other particles and organic materials, sinking to the bottom of the water and bonding with other sediments. As a result, the concentration of heavy metals in sediment is usually higher than in water [20].

The accumulation of metals in sediments, both from natural and anthropogenic sources, occurs in the same way, including rock weathering, soil erosion or dissolution of water-soluble mineral salts, making it difficult to identify and determine the origin of heavy metals. in sediment. In addition, total metal concentrations often do not accurately reflect their properties and toxicity.

The assumption of using total metal concentration as a

criterion for assessing the potential impact of contaminated sediments, meaning that all forms of a given metal have the same impact on the environment, is untenable [21].

Concentration of Pb and Cd In Clam Meat

The average concentration of the heavy metal Pb in the clams meat at the Tambak Cemandi pond station is 3.1 mg/Kg, while the average value of Cd concentration in the clams meat at the Banjar Kemuning station was lower, 2.83 mg/Kg. The average value of the heavy metal Cd concentration in the clams meat at the Cemandi pond station was 1.01 mg/Kg, while the average value at the Banjar Kemuning station was higher, 1.37 mg/Kg (Table- 3).

Table-3. Concentration of Pb and Cd in Blood Clams

No Station Heavy

Pb 3,1±0,086

2 Tambak Cemandi

Cd 1,01±0,098

Banjar Kemuning 1.37±0,294

The concentration of the heavy metal lead in shellfish biota at both observation stations exceeded the threshold set in the Indonesian National Standard (SNI 7387:2009) regarding the maximum limit for heavy metal contamination in food. The quality standard for lead in food is 1.5 mg/Kg.

The heavy metal lead (Pb) is generally a pollutant in aquatic and terrestrial ecosystems. The heavy metal lead, if ingested by humans, is very dangerous if it exceeds the maximum threshold because it can cause various diseases. Its accumulation in the human body adversely affects the circulatory, cardiovascular, renal, endocrine, digestive, immune and reproductive systems. Pb metal is neurotoxic and can spread throughout the human body and cause damage. Pb toxicity is caused by its ability to self- substitute with divalent cations thereby affecting cell function and the formation of free radicals [22].

The concentration of the heavy metal cadmium in shellfish biota at both observation stations also exceeds the threshold set in the Indonesian National Standard (SNI 7387:2009) regarding the maximum limit for heavy metal contamination in food. The quality standard for the heavy metal cadmium in food is 1 mg/kg.

If the heavy metal cadmium enters the human body, it is very dangerous, if it exceeds the maximum value it can cause various diseases. Cd metal that accumulates in the body damages kidney and bone function and causes cardiovascular disease, type 2 diabetes and cancer. The kidney is a human organ that is very sensitive to cadmium toxicity because it causes tubular dysfunction and kidney damage over time. Cd metal toxicity also causes bone disease due to bone demineralization. Accumulation of Cd metal can cause cancer such as kidney cancer, prostate cancer, breast cancer and uterine cancer because it is carcinogenic.

Carcinogenesis is caused by several factors, namely repression of gene expression, inhibition of DNA damage repair and apoptosis, induction of oxidative stress, endocrine disruption, cell proliferation, and the formation of reactive oxygen species [22].

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Maximum Tolerable Intake (MTI)

Based on the calculation results, the maximum weekly intake (MWI) value for the heavy metal Pb that can be consumed by children is 375 µg or 0.375 grams per week, while the MWI for the heavy metal Pb that can be consumed by adults is 1250 µg or 1.25 grams per week.

The MWI value of the heavy metal Cd that can be consumed by children and adults (weighing 50 kg) per week is 105 µg or 0.105 grams and 350 µg or 0.35 grams respectively (Table-4).

Furthermore, the maximum tolerable intake (MTI) value of the heavy metal Pb that can be consumed by children and adults is 0.13 kg and 0.42 kg per week, respectively. The MTI value of the heavy metal Cd that can be consumed by children and adults is 0.08 kg and 0.29 kg per week, respectively (Table-5).

Table-4. Maximum weekly intake of blood clams

Category Pb Cd

Children 0,375 0,105

Adults 1,250 0,350

Table-5. Maximum tolerable intake of blood clams

Category Pb Cd

Children 0,13 0,08

Mature 0,42 0,29

The MTI value is used as a reference for weekly consumption limits for blood clams obtained from the waters of Tambak Cemandi and Banjar Kemuning. If individuals with an average body weight of 50 kg (for adults) and 15 kg (for children) consume blood clams that exceed the MTI value, the heavy metal Pb can be toxic for those who consume it. Acute lead poisoning can cause impaired brain function, growth, impaired liver and kidney function and reproductive disorders. The lethal dose for humans is estimated to occur if 500 mg or 0.5 grams of Pb is absorbed into the body. The heavy metal Cd that enters the body exceeds the MTI value and will result in impaired kidney function, nervous and reproductive system disorders, carcinogenic risk and prostate cancer in humans [23]

Fish meat is contaminated with heavy metals, even in small concentrations, but if consumed continuously it will accumulate in the human body and become poisonous. The accumulation of heavy metals Pb and Cd in the human body can have an impact on health.

Some of the impacts include damage to the lungs, kidneys, liver and bones, neurological symptoms such as visual disturbances, ataxia, paresthesia, neurasthenia, hearing loss, dysentery, mental decline, tremors, motor disorders, paralysis and death [24].

The Relationship Between Heavy Metal Concentration In Water and Sediment with In Blood Clam

Data correlation analysis was carried out to determine whether or not there was a relationship between heavy metal concentrations in water, sediment and blood clams at the research location i.e. Tambak Cemandi and Banjar Kemuning, Sedati District, Sidoarjo Regency. If the significance value of the test results is more than 0.05 (sig > 0.05), then there is no relationship, and if the significance value is less than 0.05 (sig < 0.05), then there is a relationship between the variables [25].

The results of the Pearson correlation test for the relationship between lead (Pb) levels in water and blood clam lead (Pb) shows a Pearson correlation value of 0,737 which shows a positive relationship value, meaning that when the value of the heavy metal concentration of Pb in water increases, the value of the concentration of The heavy metal Pb in blood clams also experienced an increase and was classified as a very strong correlation criterion (0.60-0.799). The PValue (sig.) of 0,095 is greater than α = 0,05, so it can be said that the relationship between lead (Pb) levels in water and blood clams lead (Pb) levels is not significant (Table-6)

Table-6. Correlation between concentration Pb in water and blood clams

Water Biota

Water

Pearson correlation 1 .737

Sig. (2-tailed) .095

N 6 6

Biota

Pearson correlation .737 1

N 6 6

The results of the Pearson correlation test for the relationship between lead (Pb) concentration in sediment and blood clam shows a Pearson correlation value of 0,752 which shows a positive relationship value, meaning that when the heavy metal concentration of water pb increases, the value of the concentration of The heavy metal Pb in blood clams also experienced an increase and was classified as a very strong correlation criterion (0,60- 0,799). The PValue (sig.) of 0,085 is greater than α = 0,05, so it can be said that the relationship between lead (Pb) concentration of sediment and blood clam lead (Pb) concentration is not significant as shown in Table-7.

Table-7. Correlation between concentration Pb in sediments and blood clams

Sediment Biota Sediment

Pearson

correlation 1 .752

N 6 6

Biota

Pearson

correlation .752 1

N 6 6

The results of the Pearson correlation test for the relationship between cadmium (Cd) levels in water and blood clams shows a Pearson correlation value of -0,639 which shows a negative relationship value, meaning that when the value of the heavy metal Cd concentration in water rises, then the value of the heavy metal Cd concentration in blood clams will decrease, on the contrary when the value of the heavy metal Cd concentration in water decreases, the value of the heavy metal Cd concentration in blood clams will increase and is classified as a very strong correlation criterion (0,60-0,799). The PValue (sig.) of 0,172 is greater than α = 0,05, so it can be said that the relationship between cadmium (Cd) levels in water and blood clams cadmium (Cd) levels is not significant (Table-8).

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Table-8. Correlation between concentration Cd in water and blood clams

Water Biota

Water

Pearson correlation 1 -.639

N 6 6

Biota

Pearson correlation -.639 1

N 6 6

The results of the Pearson correlation test for the relationship between cadmium (Cd) concentration in sediment and blood clam shows a Pearson correlation value of -0,097 which shows a negative relationship value, meaning that when the value of the heavy metal Cd concentration in sediments increases, then the value of the heavy metal Cd concentration in blood clams will decrease, on the contrary when the value of the heavy metal Cd concentration in the sediment decreases, the value of the heavy metal Cd concentration in blood clams will increase and is classified in the very low correlation criteria (0.00-1,199) PValue (sig.) of 0,855 is greater than α = 0,05, so it can be said that the relationship between sediment cadmium (Cd) concentration and blood clam cadmium (Cd) concentration is not significant as shown in Table-9.

Table-9. Correlation between concentration Cd in sediments and blood clams

Sediment Biota

Sediment

Pearson

correlation 1 -.097

N 6 6

Biota

Pearson

correlation .097 1

N 6 6

Based on the statistical analysis of Pearson's correlation that has been carried out, it can be seen that the relationship between the metal concentration of water and sediment and blood clams on the heavy metals Pb and Cd showed no significant results.

Heavy metals have a long half-life in the body of marine biota and have a high concentration factor value in the body of marine biota. Heavy metals that enter the waters above the permissible limit value contaminate seawater and also precipitate in sediments which have a residence time of up to thousands of years. Due to bioaccumulation, heavy metals also accumulate in living organisms [26].

The presence of heavy metals in waters is directly harmful to aquatic life, which in turn indirectly affects human health. This refers to the nature of heavy metals which are difficult to break down, so heavy metals accumulate in water and are difficult to remove naturally.

Heavy metals can accumulate in aquatic life such as crustaceans and fish, as well as in sediments [27]. The accumulation of heavy metal lead (Pb) in organisms is closely related to the type of metal and the detoxification

mechanism in organisms, because heavy metal lead (Pb) is a non-essential heavy metal so it is toxic, so it cannot be used in metabolic processes and eventually accumulates.

In addition to toxicity, heavy metals accumulate in sediments and biota under the influence of gravity [28].

The half-life of heavy metals in water is 32×10³ years and in sediments 2.5×10⁸ years longer than heavy metals on land and in air. Because the residence time of heavy metals in sediments is very long, sediments contaminated with heavy metals such as Pb, Cd, and Cu have the potential to be a source of release back into seawater, and this release depends on the pH of seawater.

that the age of the blood clam can also affect the low concentration of heavy metals in the body of the blood clam, where the larger the size of the blood clam, the heavy metal concentration will decrease. Small, or younger, blood clams have a greater accumulation capacity than larger, or older, clams. The bigger the size (older) of the clams, the better their ability to eliminate heavy metals. When the metabolic process reaches its peak, the need for heavy metals also increases. As a result, the concentration of heavy metals in the trays during the production period was higher (average size) compared to small and large trays [29].

Heavy metals are considered as the most toxic substances, among other pollutants that pollute the marine environment. The presence of heavy metals in the environment can cause environmental pollution because they cannot be decomposed by biological or chemical processes. In aquatic environments, heavy metals usually accumulate in sediments and aquatic life. That 90% of heavy metals that pollute water are embedded in sediments. Heavy metal concentrations in water bodies vary according to season. The amount of heavy metals present in the bodies of aquatic organisms accumulates depending on the chemical action of these heavy metals and tends to bind to proteins and lipids in biological tissues. The type of protein that is the main target for heavy metal binding is protein, which is a protein that contains metals in its protein structure and divides the mechanism of heavy metal toxicity into three mechanisms, i.e. production of reactive oxygen species and the Fenton reaction, inhibition of functional groups in biomolecules, and transfer of metal ions essential for biomolecules [30].

CONCLUSIONS

The average concentration of Pb and Cd at the research station has exceeded the established safe limits.

Pb and Cd levels in the waters of station Tambak Cemandi were 2.5 ppm & 1.14 ppm, while at station Banjar Kemuning were 1.96 ppm & 0.75 ppm. The water quality standards for Pb and Cd were 0.03 and 0.01 ppm, respectively, based on the Government Regulation of the Republic of Indonesia Number 82 of 2001 concerning Quality Management and Control of Water Pollution.

Pb and Cd levels in sediment at station Tambak Cemandi were 14.44 mg/kg & 2.9 mg/kg, while at station Banjar Kemuning were 11.81 mg/kg & 2.5 mg/kg. The quality standard for the heavy metal lead and cadmium in sediment were 25 mg/Kg and 0.2 mg/kg, respectively, according to the Swedish Environmental Protection Agency (SEPA) 2000.

Pb and Cd levels in blood clams at station Tambak Cemandi were 3.1 mg/kg & 1.01 mg/kg, while at 15

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station Banjar Kemuning were 2.83 mg/kg & 1.37mg/kg, exceeded maximum limit for heavy metal contamination in food. The quality standard for lead and cadmium in food is 1.5 and 1 mg/Kg, respectively.

Maximum Tolerable Intake (MTI) Pb and Cd values in children are 0.13 kg/week & 0.08 kg/week, and in adults are 0.42 kg/week & 0.29 kg/week. The results of Pearson correlation analysis show that there is no significant relationship between concentration of Pb and Cd in water and concentration of Pb and Cd in sediment and blood clams at the Tambak Cemandi and Banjar Kemuning research locations, Sidorjo Regency.

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